JP2589049B2 - Novel trifluoromethoxyfluoropropanes 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 process for producing trifluoromethoxyfluoropropanes which does not contain chlorine atoms and does not destroy ozone in the ozone layer, and 1-trifluoromethoxy-2,2,3,3,3- It relates to pentafluoropropane.

[0002]

2. Description of the Related Art Conventionally, chlorofluorocarbon (hereinafter abbreviated as CFC) is best known as a refrigerant, a blowing agent and a solvent. CFCs are widely used in various industrial fields because of their low toxicity, nonflammability, and chemical and thermal stability.

However, C having such excellent characteristics
It has been pointed out that FC, when released into the atmosphere, destroys the stratospheric ozone layer, and therefore has a serious adverse effect on ecosystems on earth, including humans.

In order to deal with such global environmental problems,
There is a need for compounds that can replace CFCs that can be used as refrigerants, blowing agents and solvents that have little or no effect on the global environment when released into the atmosphere.

On the other hand, fluorine-containing ethers can be considered as an alternative compound of CFC. As a method for producing the trifluoromethoxyfluoroalkanes, a fluoroformate derived from a fluoroalcohol and a fluorophosgene is fluorinated with sulfur tetrafluoride [US Pat.
No. 80, J.M. Org. Chem. , Vol. 29, P1
1-15 (1964)], a chlorination reaction of the corresponding methyl ethers, followed by fluorination with antimony trifluoride [J. Fluorine Chem. , Vol. 1
1, P93-107 (1978), ibid. , Vo
l. 13, P123-140 (1979)], an addition reaction of trifluoromethylhypofluoride with a fluorine-containing olefin compound [J. Org. Chem. , Vol. 4
8, P242-250 (1983)], and the reaction of diethyl sulfate with fluorophosgene in the presence of potassium fluoride (U.S. Pat. No. 3,505,410). Among these conventional production methods, SF ₄ used as a raw material is a compound that is extremely difficult to use industrially, and a by-product of the reaction is also a sulfur-containing compound. . In the chlorination reaction of, a plurality of isomers of chlorinated products are formed and it is difficult to separate them. In addition, two types of products are obtained depending on the orientation of the addition reaction, and a separation operation is required. Although a single product can be obtained, the range of applications for producing a similar compound is narrow because the raw materials are limited.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for efficiently synthesizing fluorine-containing ethers and a novel compound 1-trifluoromethoxy-2,2,3,3,3-.
It is in providing pentafluoropropane.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, fluorine-containing ethers, especially trifluoromethoxyalkanes, are effective alternatives to the conventional CFCs. And as a result of intensive research, fluorophosgene

Embedded image COF ₂ (I) and a general formula

Embedded image R ¹ —OSO ₂ —R ² (II) (wherein R ¹ represents a fluorine-containing alkyl group having 3 carbon atoms, and R ² represents an alkyl group or a fluorine-containing alkyl group) By reacting with an ester compound in an aprotic polar solvent or in the absence of a solvent in the presence of an alkali metal fluoride or an alkaline earth metal fluoride, a relatively good conversion and high selectivity can be synthesized. They have found and completed the present invention.

Specific examples of the sulfonic acid ester compound represented by the general formula (II) used as a raw material in the present invention include, for example, 2,2,3,3,3-pentafluoropropyltrifluoromethanesulfonate and 2 And fluorinated propyl trifluoromethanesulfonates such as 2,2,3,3-tetrafluoropropyltrifluoromethanesulfonate.

In the present invention, fluorophosgene (I)
The reaction between the compound and the sulfonic acid ester compound represented by the general formula (II) is performed in an aprotic polar solvent or in the absence of a solvent. Examples of the aprotic polar solvent include monoglyme [CH ₃ OCH ₂ CH ₂ OCH ₃ ], diglyme [CH ₃ O (CH ₂ CH ₂ O) ₂ CH ₃ ], triglyme [CH ₃ O (CH ₂ CH ₂ O) Ethers such as ₃ CH ₃ ], tetraglyme [CH ₃ O (CH ₂ CH ₂ O) ₄ CH ₃ ], diethyl ether, dibutyl ether, dioxane; nitriles such as acetonitrile; dimethylformamide;
Examples include amides such as dimethylacetamide,
It goes without saying that the present invention is not limited to this.

In the present invention, an alkali metal fluoride or an alkaline earth metal fluoride is used as a catalyst. As the alkali metal fluoride, for example, sodium fluoride, potassium fluoride, cesium fluoride, or the like is used. As the alkaline earth metal fluoride, for example, calcium fluoride or the like is used. Alkali metal fluorides are preferred from the viewpoint of the yield.

The amount of the alkali metal fluoride or alkaline earth metal fluoride to be used is not particularly limited, and is 0.1 to 4.0 moles per mole of fluorophosgene (I).
It is preferable to select from a range of 1.0 to 1.5 times mol.

In the reaction of the present invention, the ratio of fluorophosgene (I) to the sulfonate compound represented by the general formula (II) is not particularly limited, and the reaction can be carried out at any ratio. However, in order to improve the conversion of fluorophosgene (I), the reaction is preferably carried out with an excess of the sulfonic acid ester compound represented by the general formula (II).

The pressure in the reaction of the present invention is not particularly limited, and the reaction proceeds at any pressure from reduced pressure to increased pressure. When the reaction is performed under pressure, the pressure is not particularly limited, but it is 50 kg / cm from the viewpoint of operability and the like.
It is preferably at most ² G.

The reaction temperature in the reaction of the present invention varies depending on the reaction time, the reaction pressure, the amount of the catalyst and the like.
0 ° C, preferably selected from the range of 20 to 100 ° C.

The reaction time in the reaction of the present invention varies depending on the reaction temperature, reaction pressure, amount of catalyst, etc., but the reaction is almost completed within several hours to several tens of hours.

[0016]

EXAMPLES Hereinafter, production examples of the trifluoromethoxyfluoropropanes of the present invention will be described with reference to examples. General formulas listed here

The sulfonic ester compound represented by R ¹ -OSO ₂ -R ² (II) is obtained by reacting a corresponding commercially available fluorinated alcohol with trifluoromethanesulfonic anhydride [Tetrahedron, vol. 4
4, P5375-5387 (1988); Org.
Chem. , Vol. 49, P2258-2273 (1
984)] or reaction with trifluoromethanesulfonic acid fluoride [J. Org. Chem. , Vol. 3
0, P4322-4324 (1965), Tetrah
edron, vol. 21, P1-4 (1965)]. Of course, the present invention is not limited by the following examples.

Example 1 A 1,000 ml stainless steel reactor equipped with a stirrer, a pressure gauge, a thermometer, a gas inlet pipe and a gas outlet pipe was placed in a 2,2,3
136 g (0.485 mol) of 3,3-pentafluoropropyltrifluoromethanesulfonate, 42.3 g (0.728 mol) of spray-dried potassium fluoride, 210 m of dried diethylene glycol dimethyl ether
After degassing, 32 g (0.485 mol) of fluorophosgene was added from the gas inlet tube and sealed. The temperature was gradually raised and maintained at a reaction temperature of about 70 ° C. for 60 hours. Thereafter, another stainless steel container was connected to the reactor, and the reaction product was transferred to this container under reduced pressure. This was washed with ice water, dilute aqueous potassium hydroxide solution and saturated saline in this order, dried over anhydrous magnesium sulfate, and distilled to obtain a colorless transparent liquid having a boiling point of 26 ° C.
3.5 g (41% yield) were obtained.

From ¹ H-NMR and ¹⁹ F-NMR spectra, 1-trifluoromethoxy-2,2,3,3
It was found to be 3-pentafluoropropane.

The ¹ H-NMR and ¹⁹ F-NMR spectrum data are shown below. In addition, ¹ H-NMR and ¹⁹ F-
For the measurement of the NMR spectrum, deuterated chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as internal standard substances, respectively.

¹ H-NMR (CDCl ₃ ) δ 4.34 (2
_{H, t, J HF = 11.9Hz} , - CH 2 CF 2 CF 3).

¹⁹ F-NMR (CDCl ₃ ) δ-62.6
_{(3H, s, CF 3 O} -), - 84.2 (3F, s, -C
_{H 2 CF 2 CF 3),} - 124.6 (2F, t, J FH = 1
_{1.0Hz, -CH 2 CF 2 CF 3} ).

Example 2 2, 2, 3, 3 were placed in a 300 ml stainless steel reactor equipped with a stirrer, a pressure gauge, a thermometer, a gas inlet tube and a gas outlet tube.
-47.0 g (0.18 mol) of tetrafluoropropyl trifluoromethanesulfonate, 10.5 g (0.18 mol) of spray-dried potassium fluoride and 53 ml of dried diethylene glycol dimethyl ether were deaerated, and then fluorophosgene 12. 0g
(0.18 mol) and sealed. The temperature was gradually raised and maintained at a reaction temperature of about 70 ° C. for 69 hours. Thereafter, another stainless steel container was connected to the reactor, and the reaction product was transferred to this container under reduced pressure. This was washed with ice water, dilute aqueous potassium hydroxide solution and saturated saline in this order, dried over anhydrous magnesium sulfate, and distilled to obtain 24.4 g of a colorless transparent liquid having a boiling point of 46 ° C.
(68% yield).

From the ¹ H-NMR and ¹⁹ F-NMR spectra, it was found to be 1-trifluoromethoxy-2,2,3,3-tetrafluoropropane.

The ¹ H-NMR and ¹⁹ F-NMR spectrum data are shown below. In addition, ¹ H-NMR and ¹⁹ F-NM
For the measurement of the R spectrum, deuterated chloroform was used as a solvent, and tetramethylsilane and trichlorofluoromethane were used as internal standard substances, respectively.

¹ H-NMR (CDCl ₃ ) δ 4.30 (2
H, t, J _HF = 11.9 Hz, t, J _HF = 1.3 Hz,
_{- CH 2 CF 2 CHF 2)} , 5.91 (1H, t, J HF =
_{53.1Hz, t, J HF = 4.0Hz} , -CH 2 CF 2 C
HF ₂ ).

[0026]¹⁹F-NMR (CDCl_Three) Δ-62.6
(3F, s,CF ₃ O-), -125.3 (2F, t, J
_FH= 11.1 Hz, -CH_Two CF ₂ CHF_Two),-13
8.8 (2F, d, J_FH= 53.3Hz, -CH_TwoCF_Two
CHF ₂ ).

[0027]

The trifluoromethoxyfluoropropanes produced in the present invention include, for example, 1-trifluoromethoxy-2,2,3,3,3-pentafluoropropane and 1-trifluoromethoxy-2,2,3. , 3-tetrafluoropropane has a boiling point of 26 ° C. and 46 ° C., respectively, and can be used for applications such as a solvent and a foaming agent, like the conventional CFC, and is extremely useful as a substitute for CFC. Moreover, since it contains a hydrogen atom, it has high reactivity with hydroxyl radicals in the atmosphere and is easily decomposed in the troposphere, so that it has a small greenhouse effect. Since it does not contain chlorine atoms, it does not destroy the ozone layer and has little effect on the global environment.

 ──────────────────────────────────────────────────続 き Continued on the front page (73) Patent owner 000002004 Showa Denko Co., Ltd. 1-13-9 Shiba-Daimon, Minato-ku, Tokyo (73) Patent owner 000000044 Asahi Glass Co., Ltd. 2-1-2 Marunouchi, Chiyoda-ku, Tokyo (73) Patent holder 000174851 Mitsui-DuPont Fluorochemicals Co., Ltd. 1-18-18 Sarugaku-cho, Chiyoda-ku, Tokyo (73) Patent holder 000003300 Tosoh Corporation 4560 Kaiseicho, Shinnanyo-shi, Yamaguchi Prefecture Name agent Attorney Eiji Tomomatsu (1 outsider) (72) Inventor Yoshihiko Goto 6-40th floor Hongo Wakai Building 2-40-17 Hongo, Bunkyo-ku, Tokyo Room for New Generation Refrigerant Project, National Institute for Global Environmental Technology (72) Inventor Shiro Yamashita Hongo Wakai Building 6F, Hongo 2-40-17 Hongo, Bunkyo-ku, Tokyo Room (72) Inventor Haruaki Ito 2-40-17 Hongo, Bungo-ku, Tokyo Hongo Wakai Building 6th Floor New Generation Refrigerant Project Room, Foundation for Global Environmental Technology, Japan (72) Inventor Suga Atsuo Hongo Wakai Building 6F, Hongo Wakai Building, 2-40-17 Hongo, Bunkyo-ku, Tokyo Room (72) Inventor Yuji Mochizuki 2-40-17 Hongo, Hongo, Bunkyo-ku, Tokyo 6th floor of the building New Generation Refrigerant Project, Room for Research Institute of Innovative Technology for the Environment (72) Inventor, Nagataka Nobutaka 2-40-17 Hongo, Bungo-ku, Tokyo Hongo Wakai Building 6th floor 6th floor Refrigerant Project Room (72) Inventor Akira Sekiya 1-1-1 Higashi, Tsukuba City, Ibaraki Pref.

Claims (3)

(57) [Claims] 1. A fluorophosgene represented by the chemical formula: COF ₂ ... (I) and a general formula: R ¹ —OSO ₂ —R ² ... (II) (R ¹ has three carbon atoms) With a sulfonic acid ester compound represented by the formula: R ² represents an alkyl group or a fluorine-containing alkyl group) in an aprotic polar solvent or in the absence of a solvent, in an alkali metal fluoride or an alkaline earth metal. Trifluoromethoxyfluoropropane represented by the general formula: CF ₃ O—R ¹ (III) wherein R ¹ is the same as defined above, wherein the reaction is carried out in the presence of a fluoride. Manufacturing methods. 2. A wherein formula (II), R ¹ is embedded image _{C 2 H X F 5-X} CH 2 - ( wherein, x is an integer from 0 to 5) using a sulfonic acid ester consisting of The method for producing trifluoromethoxyfluoropropanes according to claim 1. 3. 1-trifluoromethoxy-2,2,3 represented by the formula: CF ₃ —O—CH ₂ —CF ₂ —CF ₃ (IV)
3,3-pentafluoropropane.