JPH02204437A - Production of trihydrofluoropropanes having difluoromethylene group and trihydrochlorofluoropropanes - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject compounds expectable for use of blowing agent, etc., similar to fluorocarbon in high selectivity and high yield by using trihydrohalogenopropanes as raw material and fluorinating in liquid phase in the presence of HF and specific fluorinating catalyst. CONSTITUTION:Trihydrohalogenopropanes having dihalogenomethylene group expressed by formula I (0<=m<=2) such as 1,1,2,2,3-pentachloropropane or 1,1,1,2- tetrachloro-2-fluoropropane is fluorinated by reacting with HF in the presence of catalyst composed of at least one halide of niobium, tantalum or antimony such as niobium pentachloride, antimony pentachloride or tantalum pentafluoride in liquid phase at 0-200 deg.C in normal pressure or under pressure to afford the aimed compounds expressed by formula II (2<=n<=5) such as 1,1,3-trichloro-2,2- difluoropropane expected of similar use as fluorocarbon such as coolant or detergent.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to trihydrofluoropropanes having a difluoromethylene group and trihydrochloropropanes (C3H3Cl 5>゛.FI,;
2≦n≦5).

Trihydrofluoropropanes and trihydrochlorofluoropropanes having a difluoromethylene group can be used as blowing agents, refrigerants,
It is expected to be used as a cleaning agent.

[Prior Art and Problems to be Solved by the Invention 1 Conventionally known synthetic routes for trihydrofluoropropanes and trichlorofluoropropanes having a difluoromethylene group include, for example, synthesis of tetrafluoroethylene and methanol. to 2.2.3.3-tetrafluoropropanol, which is then reacted with sulfuryl chloride to give a chlorosulfonic acid ester, which is then reacted with an alkali metal chloride to give 1-chloro-2
, 2,3,3-tetrafluoropropane requires multiple steps, making it difficult to improve the yield and making it unsuitable for industrial production.

[Means for Solving the Problems] The present inventor has developed a method for producing l-sushi-dorofluoropropanes and tri-sushi-dorofluoropropanes (C3HaC1s-, F,; 2≦n≦5) having a difluoromethy1/one group. As a result of intensive research into efficient production methods, trihydrohalogenoprobanes (C3H3Cl5--F-;
0≦m≦2) with hydrogen fluoride in the presence of a catalyst consisting of at least one of niobium, tantalum, and antimony halides, chlorine is replaced with fluorine to form trihydrofluorocarbon having a difluoromethylene group. It was discovered that propanes can be produced, and the present invention was provided.

The details of the present invention will be explained below along with examples.

That is, ■・Lihydrohalogenoprobanes (C3Ha
When C1s-, F, ;O≦m≦2) is fluorinated with hydrogen fluoride in the liquid phase, trihydrofluoropropanes having a difluoromethylene group, (CsH
It was found that aCt 5-Frl; 2≦n≦5, man) was produced in good yield.

F C3HaC15--F--= C3H3Cls-, F
nO≦Melon≦2 2≦n≦5an In this reaction, halides of niobium, tantalum, and antimony, such as niobium fluoride, niobium chloride, tantalum pentafluoride, tantalum pentachloride, antimony pentafluoride, antimony pentachloride, Fluorination catalysts such as antimony dichloride trifluoride and andimony dibromide trifluoride can be used.

The fluorination reaction is carried out in a liquid phase at medium pressure or under pressure, with a temperature of 0 to 20
It is appropriate to conduct the reaction at a temperature of 0°C, particularly preferably from room temperature to 150°C.

In the present invention, the reaction is usually carried out without a solvent, but a solvent may also be used. In this case, the solvent used is one that dissolves the raw material propane and is more difficult to fluorinate than the raw material. Although not particularly limited, it is usually appropriate to carry out the reaction at a pressure of 0 to 10 kg/cd, and when a solvent is used, the reaction pressure varies depending on the type of solvent, etc.

Hydrogen fluoride may be charged in advance before the reaction, but it is preferable to blow it into the liquid phase during the reaction.

1-Helihydrohalogenoprobanes (C3) used as raw materials
13Cls --F, ; O≦m≦2), 1.1.2゜2.3-pentachloropropane (R-2
40aa), 1,1.1.2.2-pentachloropropane (R-240ab), 1.1.2.3-tetrachloro-2-fluoropropane (R-241ba), 1.1.
t, 2-tetrachloro-2-fluoropropane (R
-241bb), 1,1.3-) Richloro2,2-difluoropropane (R-242ea), i, i, i
-Trichloro-2,2-difluoropropane (R-24
2eb), all of which are known compounds.

Trihydrofluoropropanes and trihydrochlorofluoropropanes (CsHaCt 5-nF,; 2≦n≦) having a difluoromethylene group produced by the reaction
5), 1.1.3-1-lichloro-2゜2-di-fluoropropane (R-242ca), 1,1゜1-
Trichloro-2,2-difluoro70pan (R-242
cb), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,
2,3-trifluoropropane (R-243cb), 1
, 1-dichloro-1,2,2-)lifluoropropane (
R-243cc), 1-chloro-2,2,3,3-tetrafluoropropane (R-244ca), 1-chloro-
1,1,2,2-tetrafluoropropane (R-244
cc), 1.1.1.2°2-pentafluoropropane (R-245cb), which can be prepared by conventional methods,
For example, it can be separated by fractional distillation or the like.

[Example] Examples of the present invention will be shown below.

Example 1 In a Hastelloy C autoclave with an internal volume of 1 liter,
1.1.2.2.3-Pentachloropropane (CHCl
2cct 2CH2Cl: 50 of R240aa)
0g and 50g of antimony pentachloride, and while supplying hydrogen fluoride at a rate of 50g/hour for 3 hours,
After raising the temperature to C, hydrogen fluoride was further supplied at a rate of 50 g/hour for 3 hours, and the reaction temperature was maintained in this state for 20 hours. The 9 reactants were cooled to -78°C in a trap. was collected on. As a result of analyzing the composition of the collected material after removing the acid content using gas chromatography and IOF-NMR, it was found that CHF2CF has a difluoromethylene group.
2CH2Cl (R-244ca), CHCt F2
F2CH3Cl (R-243ca), and CHC
In addition to 2CF 2CH2CI (R-242ca), CHF 2CCI FCH2C1 (R243ba
), CHCtFCCI FC82C1 (R242ba)
, CHCl eccL FCH2Ct (R-241
ba), CHCl FCCl 2C82Cl (R-2
240 having two or more fluorine atoms such as 41aa)
It was confirmed that CFCs were generated. The main results are shown in Table 1.

Table 1. Fluorination of R-240aa-243ba), CCI F2CCl FCH3 (
R-243bc), CF30C12CH3 (R243
ab), CC1F2CCl FCH3 (R243
bC), CCI F2CC12CH3 (R242a
It was confirmed that fluorocarbons in the 240 range having two or more fluorine atoms, such as C), were produced.

The main results are shown in Table 2.

Table 2 Fluorination Example 2 of R-240ab 1,1.2.2.3-pentachloropropane (R-24
0aa) instead of i, i, i, 2.2. A reaction was carried out under the same conditions as in Example 1, except that 500 g of -pentachloropropane (R-240ab) was used, 50 g of tantalum pentafluoride was used instead of antimony pentachloride, and the reaction temperature was changed to 120°C. As a result, C F sCF 2CHs (R-245
cb), and CC1F2CF2CH3 (R-244c
In addition to CFaCCI FCH3 (R Example 3 1, 1.2.2.3-pentachloropropane (R-24
1.1.2.3-tetracDO-2 instead of 0aa)
- 500 g of fluoropropane (R-241ba),
, 50% tantalum pentachloride instead of antimony pentachloride
Example 1 except that g was used and the reaction temperature was 130°C.
The reaction was carried out under the same conditions. As a result, C HF 2 CF 2CHzCt with difluoromethylene group
(R244ea), CHCl FCF2CH2C#
, (R243ea), and CHCl2CFzCHzC
1 (R-242ca) etc. CHFzCCt FC
HzCffi (R-243ba), CHCt F
2 such as CCt F CH2Ct (R242b a )
It was confirmed that CFCs in the 240 range containing more than 3 fluorine atoms were produced. The main results are shown in Table 3.

Table 3. Fluorination of R-241ba Example 4 1,1.2.2.3-pentachloropropane (R-24
0aa) instead of 1.1.1.2. -Tetrachloro-
A reaction was carried out under the same conditions as in Example 1, except that 500 g of 2-fluoropropane (R-241bb) was used, 50 g of niobium pentachloride was used instead of antimony pentachloride, and the reaction temperature was changed to 130°C. As a result, C F sCF 2CH3 (R-245e
b), CCIF2CF2CH3 (R244cc), CC
I l! FCF2CH3 (R243cc), and CC
In addition to t3CF2CH3 (R242Cb), etc., CF
3 CC destination F CH3 (R244bb), CCt F2
CC1FCH3 (R243bC), CC12Fcci
It was confirmed that CFCs in the 240 range having two or more fluorine atoms, such as FCH3 (R242bC), were produced.

The main results are shown in Table 4.

Table 4. R-241bb fluorinated coating 5. R-24
Fluorination of 2ea Example 5 1,1.2.2.3-pentachloropropane (R, -2
40aa) instead of 1.1.3-trichloro-2,
500g of 2-difluoropropane (R-242ca)
5 of tantalum pentafluoride instead of antimony pentachloride.
Example 1 except that 0g was used and the reaction temperature was 110°C.
The reaction was carried out under the same conditions. The results are shown in Table 5.

Example 6 1,1.2.2.3-pentachloropropane (R-24
0aa) instead of 1.1.1. -trichloro-2,2
- 500 g of difluoropropane (R-242cb) was reacted under the same conditions as in Example 1, except that the reaction temperature was 110°C. The results are shown in Table 6.

Table 6. Fluorination of R-242cb [Effects of the Invention] The present invention produces trihydrofluoropropane having a difluoromethylene group by reacting trihydrohalogenopropanes as raw materials with hydrogen fluoride in the presence of a fluorination catalyst in a liquid phase. It has the effect of producing trihydrochlorofluoropropanes and trihydrochlorofluoropropanes.

Claims (1)

[Claims] 1. Trihydrohalogenopropanes having a dihalogenomethylene group (C_3H_3Cl_5_-_mF_m;0
≦m≦2) with hydrogen fluoride in the presence of a catalyst consisting of at least one of niobium, tantalum, and antimony halides, and trihydrofluoropropanes and trihydrochloro having a difluoromethylene group. Fluoropropanes (C_3H_3Cl
_5_-_nF_n; 2≦n≦5, m<n) manufacturing method. 2. The fluorination reaction is carried out under normal pressure or liquid phase pressure, from 0 to 20
The manufacturing method according to claim 1, which is carried out in a temperature range of 0°C. 3. Trihydrohalogenopropanes are 1, 1, 2, 2,
The manufacturing method according to claim 1 or 2, wherein 3-pentachloropropane is used. 4. Trihydrohalogenopropanes are 1,1,1,2,
The manufacturing method according to claim 1 or 2, wherein 2-pentachloropropane is used. 5. Trihydrohalogenopropanes are 1,1,2,3-
The manufacturing method according to claim 1 or 2, wherein tetrachloro-2-fluoropropane is used. 6. Trihydrohalogenopropanes are 1,1,1,2-
The manufacturing method according to claim 1 or 2, wherein tetrachloro-2-fluoropropane is used. 7. The production method according to claim 1 or 2, wherein the trihydrohalogenopropane is 1,1,3-trichloro-2,2-difluoropropane. 8. The manufacturing method according to claim 1 or 2, wherein the trihydrohalogenopropane is 1,1,1-trichloro-2,2-difluoropropane.