JPH0977702A - New fluorine-containing olefin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new fluorine-containing olefin which is useful as a monomer for polymers and as an intermediate for a variety of fluorine-containing compounds, for example, hydrofluorocarbons, medicines and agrochemicals. SOLUTION: This fluorine-containing olefin is represented by formula I [X is chlorine, fluorine; Y is chlorine, bromine, iodine; R<1> and R<2> are each H, a 1-10C alkyl or R<1> and R<2> link to each other to form the group of the formula: -(CH2 )n - (n is 3-7)], typically 3-trifluoromethyl-1,1,1-trifluoro-2,4-dichloro-2-butene. The compound of formula I is obtained by reaction of a compound of formula II (Rf and Rf' are each trifluoromethyl; Z is hydroxyl, sulfonate group) with a halogenating agent (for example, in the case that Z is OH, the agent is a hydrogen halide, phosphorus halide, while in the case that Z is a sulfonate, it is an alkali halide).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compound, a fluorine-containing olefin, and a process for producing the same.
The fluorinated olefin according to the present invention is useful in various industrial fields, and can be used as a polymer monomer itself or as an intermediate for various fluoro compounds such as hydrofluorocarbons and medical and agricultural chemicals.

[0002]

The olefin in the present invention is a novel compound, and its production method has not been known so far.

[0003]

The olefins containing fluorine are useful in various industrial fields, but those currently industrially produced are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and their products. It is limited to dimers and trimers.

[0004]

Means for Solving the Problems The present inventor can easily obtain a high yield of a fluorine-containing olefin represented by the following formula (3) by reacting a compound represented by the following formula (2) with a halogenating agent. The inventors have found that they can be obtained at a rate, and have completed the present invention.

[0005]

Embedded image [Here, X is chlorine or fluorine. Z is a hydroxyl group or a sulfonate group. R ¹ and R ² represent the same or different hydrogen or an alkyl group having 1 to 10 carbon atoms, or are connected to each other to represent — (CH ₂ ) _n — (where n is 3
~ Integer 7). Rf and Rf ′ are the same or different and are fluorine or C _n F _{2n + 1} (where n is an integer of 1 to 7)
Or- (CF ₂ ) _m- representing by connection (m is an integer of 1 to 4). ]

[0006]

Embedded image [Where Z is chlorine or bromine or iodine. Z,
R ¹ , R ² , Rf, and Rf ′ are the same as in the above formula (2). ]

The compound (2) which is a raw material of the present invention is a compound in which Y is a hydroxyl group, for example, hexachloro-
2,3-Dichloro-1,1,1,4,4,4-hexafluoro-2 obtained by fluorinating 1,3-butadiene
It can be produced by radically adding an alcohol to butene and then dehydrochlorinating with an alkali or the like. When Y is a sulfonate group, it can be produced by reacting the alcohol thus obtained with a sulfonic acid chloride such as methanesulfonic acid chloride, paratoluenesulfonic acid chloride or trifluoromethanesulfonic acid chloride. .

As the halogenating agent used in the present invention, when Y is a hydroxyl group, for example, hydrogen halide such as hydrogen chloride, hydrogen bromide, hydrogen iodide, or phosphorus trichloride, phosphorus pentachloride, or tribromide. Examples thereof include phosphorus, phosphorus halides such as phosphorus triiodide, and thionyl halides such as thionyl chloride and thionyl bromide. Further, a sulfonic acid halogenide such as methanesulfonic acid chloride or p-toluenesulfonic acid chloride can also be used.

When Y is a sulfonate group,
Examples of the halogenating agent include alkali metal halides such as lithium chloride, sodium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, magnesium bromide and calcium bromide. When halogenating a compound in which Y is a sulfonate group with an alkali metal halide, the reaction may be promoted by performing halogenation in an aprotic polar solvent, and examples of the solvent include N, N-dimethylformamide, N -Methyl-2-pyrrolidone, 1,3-dimethylimidazolidine-
2-one, dimethyl sulfoxide, sulfolane and the like can be mentioned.

Regarding the amount ratio of the compound (2) to the halogenating agent, the molar ratio of the effective halogen in the halogenating agent to the compound (2) may be in the range of 1 to 30, preferably 1 to 10. It should be in the range. The reaction temperature may be room temperature to 200 ° C, preferably room temperature to 100 ° C. Further, the compound obtained in the process of the present invention is a novel fluorine-containing olefin,
The compound represented by the following formula (1) has not been known so far.

[0011]

[Chemical 6] [Here, Y is chlorine, bromine, or iodine. X is chlorine or fluorine. R ¹ and R ² represent the same or different hydrogen or an alkyl group having 1 to 10 carbon atoms, or are connected to each other to represent — (CH ₂ ) _n — (where n is 3 to
7 integer). ]

The olefin containing fluorine is useful in various industrial fields, and the novel fluorinated olefin of the present invention is also used as a monomer for polymerization and as an intermediate of various fluorine compounds such as hydrofluorocarbons, pharmaceuticals and agricultural chemicals. it can.

[0013]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. (Example 1) 10.7 g (143 mmol) of potassium chloride was added to a 100 ml four-necked flask equipped with a dropping funnel, a thermometer, and a vapor extraction tube connected to a Liebig cooling tube.
-Toluenesulfonic acid 2- (trifluoromethyl)-
3-Chloro-4,4,4-trifluoro-2-butenyl ester 13.5 g (35 mmol), N-methyl-2
-Pyrrolidone 60 ml was charged. The low-boiling substance produced was stirred out at 80 ° C. for 3 hours and extracted with steam.
26.5 g (yield 75%) of 1,1,1-trifluoro-2,4-dichloro-2-butene was obtained. The structure of 3-trifluoromethyl-1,1,1-trifluoro-2,4-dichloro-2-butene is ¹ H-NMR and ¹⁹ F-NM.
Confirmed with R.

The spectrum data of ¹ H-NMR and ¹⁹ F-NMR are shown below. Chemical shifts were based on trichlorofluoromethane. ¹ H-NMR (CDCl ₃ ) δ 6.3 ppm ( ¹ H, multiplet line), 6.5 ppm ( ¹ H, multiplet line) ¹⁹ F-NMR (neat) δ-59.7 (cis), −
62.1 ppm (3F, quartet), -63.4 (ci)
s), -64.1 ppm (trans) (3F, quartet)

(Example 2) 2-trifluoromethyl-4,4,4-trifluoro-3-chloro-2-butenol (34.4 g) was placed in a 100 ml four-necked flask equipped with a dropping funnel, a thermometer and a Dimroth condenser. (0.15 mol),
20.2 g of thionyl chloride was charged. After stirring at 80 ° C. for 3 hours and washing with a saturated aqueous solution of sodium hydrogen carbonate and water, 3-trifluoromethyl-1,1,1-trifluoro-2,4-dichloro-2-butene 33.7 g
(Yield 91%) was obtained. The structure of the obtained compound was confirmed by ¹ H-NMR and ¹⁹ F-NMR as in Example 1.

Claims (2)

[Claims] 1. A fluorinated olefin represented by the following formula (1). Embedded image [Here, Y is chlorine, bromine, or iodine. X is chlorine or fluorine. R ¹ and R ² represent the same or different hydrogen or an alkyl group having 1 to 10 carbon atoms, or are connected to each other to represent — (CH ₂ ) _n — (where n is 3 to
7 integer). ] 2. A method for producing a fluorinated olefin represented by the following formula (3), which comprises reacting a compound represented by the following formula (2) with a halogenating agent. Embedded image [Here, X is chlorine or fluorine. Z is a hydroxyl group or a sulfonate group. R ¹ and R ² represent the same or different hydrogen or an alkyl group having 1 to 10 carbon atoms, or are connected to each other to represent — (CH ₂ ) _n — (where n is 3
~ Integer 7). Rf and Rf ′ represent the same or different fluorine or C _n F _{2n + 1} (where n is an integer of 1 to 7) or are connected to each other to represent — (CF ₂ ) _m — (where m is 1 to 1). 4 integer). ] [Chemical 3] [Here, Y is chlorine, bromine, or iodine. Z,
R ¹ , R ² , Rf, and Rf ′ are the same as in the above formula (2). ]