JPH02204428A - Production of dihydrofluoropropanes and dihydrochloro-fluoropropanes bearing difluoromethylene group - Google Patents

Abstract

PURPOSE:To obtain the title substance in high yield, which can be expected the use as a coolant or the like by effecting liquid-phase fluorination of a dihydrohalogenopropane having a dihalogenomethylene group with HF in the presence of a catalyst such as Nb halide. CONSTITUTION:The fluorination of a dihydrohalogenopropane bearing a dihalogenomethylene group (C3H2Cl6-mFm; 0<=m<=3) is conducted using HF in liquid phase in the presence of a catalyst, at least one selected from the halides of Nb, Ta and Sb, at 0 to 200 deg.C under normal to elevated pressure, preferably at room temperature to 150 deg.C and 0 to 30kg/cm<2> to give the title substance (C3H2Cl6-nFn; 2<=n<=6. m<n). The reaction is usually carried out in the absence of a solvent, but a solvent which more resists to fluorination than the feedstock does may be used. HF is preferably blown into the liquid phase for reaction.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to the production of dihydrofluoropropanes and dihydrochlorofluoropropanes (C3H2Cie-1F, ; 2≦mouth≦6) having a difluoromethylene group. It is about law.

Dihydrofluoropropanes and dihydrochlorofluoropropanes having a difluoromethylene group are expected to be used as blowing agents, refrigerants, cleaning agents, etc., similar to conventionally used fluorocarbons.

[Prior art and problems to be solved by the invention] Conventional synthetic routes for dihydrofluoropropanes and dihydrochlorofluoropropanes having a difluoromethylene group include, for example, propyne (CH3
C-CH) is fluorinated with hydrogen fluoride to form 2,2-difluoropropane (CH3CF2CH3), and then only the three hydrogen atoms at the 1st position are selectively chlorinated with chlorine to obtain i.
, i, i-trichloro-2,2-difluoropropane (CC13CF2OH3) and then selectively fluorinate only two of the three chlorine atoms substituted for the 1-position carbon atom to produce 1-chloro. -1,1,2,2-
Method of synthesizing tetrafluoropropane (J, An
d, Chew, Soe, , 65.2342 (
1943), it requires multiple steps, making it difficult to improve the yield and making it unsuitable for industrial production.

[Means for Solving the Problems] The inventors have conducted extensive studies on an efficient method for producing dihydrofluoropropanes and dihydrochlorofluoropropanes (C3H2C1s-F, ; 2≦n≦6) having a difluoromethylene group. As a result, dihydrohalogenopropanes (C3H2C
15-F-; 0≦K≦3) is fluorinated with hydrogen fluoride in the presence of a catalyst consisting of at least one of halides of niobium, tantalum, and antimony, thereby replacing chlorine with fluorine and producing difluoromethylene. The inventors have discovered that dihydrofluoropropanes and dihydrochlorofluoropropanes having the same group can be produced, and have come to provide the present invention.

That is, raw material dihydrohalogenopropanes (C3H2
When C1s-mFm; 0≦K≦3) is fluorinated with hydrogen fluoride in the liquid phase, dihydrofluoropropanes having a difluoromethylene group and dihydrochlorofluoropropanes (C3H2C1-F
It was found that n: 2≦n≦6, m<n) was produced with good yield.

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

F C3H2Cl e-, F---C3H2C 6-n
In this Fn reaction, halides of niobium, tantalum, and antimony, such as niobium fluoride, niobium chloride, tantalum pentafluoride, tantalum pentachloride, antimony pentafluoride, antimony pentachloride, antimony dichloride trifluoride, and diodorous Fluorination catalysts such as andimony 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 1,50°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. 9 Reaction pressure is not particularly limited, but it is usually appropriate to carry out the reaction at 0 to 30 kg/aa, and when a solvent is used, it varies depending on the type of solvent, etc.

Hydrogen fluoride may be charged into the reactor together with the raw material propane before the reaction, but it is preferable to blow it into the liquid phase during the reaction.

Dihydrohalogenopropanes (C5H2C) used as raw materials
t 6-11Fa; o≦m≦3), ,,2
．． 2゜3-hexachloropropane (R-230ab),
1゜1,2.2.3.3-hexachloropropane (R2
30aa),,! , ,2.3-pentachloro-2-
Fluoropropane (R-231bb), 3-tetrachloro-2,2,-difluoropropane (R-23
2eb), 1゜1,3.3-tetrachloro-2,2-difluoropropane (R-232ca), 1,,3-trichloro-1,2,2-)-lifluoropropane (R-2
33cb), all of which are known compounds.

Dihydrofluoropropanes having a difluoromethylene group produced by the reaction, and dihydrochlorofluoropropanes (CsH2Ct s-,, F-: 2≦n≦
6, m<n), 3.3-tetrachloro-2
, 2-difluoropropane (R-232ca), , 3
-), lichloro, 2.2-)-lifluoropropane (R-233cb), 3-trichloro-2,2,
3-trifluoropropane (R-233ca), 1-
Dichloro-1,2,2,3-tetrafluoropropane (
R-234cd), 1,3-dichloro-1,1,2,2
-Tetrafluoropropane (R234cc), 1,1-
Dichloro-2,2,3,3-tetrafluoropropane (
R-234Cb), 1,3-dichloro-1,2,2,3
-tetrafluoropropane (R-234ca), 1-chloro-1,1,2,2,3-pentafluoropropane (
R-235cc), 3-chloro-1,1,1,2,2-
Pentafluoropropane (R-235cb), 1-riD
O-1,2,2,3,3-pentafluoropropane (R
-235ca), 2.2.3-hexafluoropropane (R-236cb), 2゜2,3.3-hexafluoropropane (R-236ca), which can be prepared by conventional methods. , for example, by fractional distillation.

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

Example 1 In a Hastelloy C autoclave with an internal volume of 1 liter,
,,2.2.3. -hexachloropropane (CC13
CC12CHC12: 500g of R230ab),
Add 50g of antimony pentachloride and add 50g of hydrogen fluoride.
After raising the temperature to 100° C. while supplying hydrogen fluoride at a rate of 50 g/hour for 3 hours, hydrogen fluoride was further supplied at a rate of 50 g/hour for 3 hours. The reaction temperature was maintained in this state for 20 hours, and the 8 reactants were collected in a trap cooled to -78°C. As a result of analyzing the composition of the collected material after removing the acid content using gas chromatography and 19F-NMR,
CF3CF2 having difluoromethylene group
CH2C1 (R-235cb), CCt F 2 CF
2 CH2Ct (R-234cc), and CC
In addition to t2FCF2CH2C1 (R-233cb), CF3CC1FCH2C1 (R-234bb), CC
tF2CCtFCHeCL (R233bc),
CClF2CCl2CH2Cl (R-232a
It was confirmed that CFCs in the 230 range having two or more fluorine atoms such as c) were produced. The main results are shown in Table 1.

Table, Fluorination Example 2 of R-230ab 1, 2.2.3. -hexachloropropane (R-2
30ab), 500 g of 2.2.3.3-hexachloropropane (R-230aa>), 50 g of tantalum pentafluoride instead of antimony pentachloride, and the reaction temperature was 120 ° C. was reacted under the same conditions as in Example 1. As a result, C HF 2CF 2 CHCI F (R-2
35ca), CHCI F CF 2CHcl F (
R-234ca), CHCl2CF2CHF2(R-
234cb), CHC12CF 2CHCIF (R-
233ca), etc. CHF2CCIFCHCI F
(R-234ba), CHCl FCCI2CH
F2 (R233aa>, CHCl FCCI FCHC
I F (R-233ba), CHF2CCl FCH
It was confirmed that CFCs in the 230 range having two or more fluorine atoms, such as CI 2 (R233bb), were produced.

The main results are shown in Table 2.

Table 2. In addition to fluorinated R-230aa C12FCF2C82C#, (R233eb), etc., CF3CCt FC82C1 (R234bb), CC
1F2CCt FCHtCl (R-233be)
, CCI 2FCCI FCHtCl (R23
It was confirmed that CFCs in the 230 range having two or more fluorine atoms such as 2bb) were produced. The main results are shown in Table 3.

Table 3. Fluorination Example 3 of R-231bb 1, 2.2.3. -hexachloropropane (R-2
30ab) instead of, 2,3-pentachloro-2
- 500 g of fluoropropane (R-231bb),
50g of tantalum pentafluoride instead of antimony pentachloride
The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 120°C.

As a result, CF3CF2 with difluoromethylene group
CH2Cl (R235cb), CClF2CF2C
82Cl (R234CC), and C Example 4 1, 2.2.3. -hexachloropropane (R-2
30ab), 5°0 g of 3-tetracoOD-2°2-difluoropropane (R-232eb)
The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 120°C. As a result, CF3CF2CH2Cl (R-2
35eb), CCI F 2CF 2CH2C1 (R
-234cc), and CC12F CF 2CH2C
The results are shown in Table 4.

Table 4. Fluorination of R-232cb The reaction was carried out under the same conditions as in Example 1 except for the following.

As a result, CHF2CF with difluoromethylene group
2CHF2 (R236ea), CHF2CF2CHCt
F (R235c a ), CHCl FCFvCH
, C1F (R-234ea), CHCt 2CF2C
It was confirmed that CFCs in the 230 range such as HF2 (R234cb) were generated.

The main results are shown in Table 5.

Table 5. Example 5 of fluorination of R-232ca 1, i, 2.2.3. -hexachloropropane (
R-230ab), 3,3-tetracC7
C7-2゜2-difluoropropane (R-232ca)
Using 500g of tantalum pentafluoride in place of antimony pentachloride, and setting the reaction temperature to 130°C, Example 6 1,...2.2.3.-Hexachloropropane (R-2
30ab>, 1-) LicroO-2,2,
500 of 3-trifluoropropane (R-233cc)
The reaction was carried out under the same conditions as in Example 1, except that g was used and the reaction temperature was 120°C. As a result, C FaCF 2C82F (R-2
36cb), CCI F 2CF 2CH3P (R-2
35cc), and CC12F CF 2CH2F
It was confirmed that CFCs in the 230 range such as (R234cd) were generated. The results are shown in Table 6.

Table 6. The reaction was carried out under the same conditions as in Example 1, except that 100 g of R-233cc niobium fluoride was used and the reaction temperature was 110°C. As a result, CF30F2CH2C with difluoromethylene group
I (R235cb), CCtF2CF, 2CH2C
It was confirmed that CFCs in the 230 range such as 1 (R-234CC) were generated. The results are shown in Table 7.

Table 7. Fluorination Example 7 of R-233cb 1, 2.2.3. -hexachloropropane (R-2
30ab) instead of, 3-) Rikuoo-1,2,
500 of 2-trifluoropropane (R-233cb)
Example 8 1, 2.2.3. -hexachloropropane (R-2
30ab) instead of , 3-tric o rho 2.2.
500 of 3-trifluoropropane (R-233ca)
g, 5 of tantalum pentafluoride instead of antimony pentachloride
Example 1 except that 0g was used and the reaction temperature was 120°C.
The reaction was carried out under the same conditions. As a result, CHF2CF2CHF2 (R236
ca), CHF2CF2CHC! F (R-235c
a), CHC! FCF2CHCI F (R-234
It was confirmed that CFCs in the 230 range such as ca) and CHCl2CF2CHF2 (R234cb) were generated.

The main results are shown in Table 8.

Table 8. It has the effect that R-233ca fluorinated fluoropropanes and dihydrochlorofluoropropanes can be produced.

[Effect of the invention]

Claims (1)

[Scope of Claims] 1. Dihydrohalogenopropanes having a dihalogenomethylene group (C_3H_2Cl_6_−_mF_m; 0≦
m≦3) with hydrogen fluoride in the presence of a catalyst consisting of at least one of halides of niobium, tantalum, and antimony, and dihydrofluoropropanes having a difluoromethylene group, and dihydrochlorofluoro Propanes (C_3H_2Cl_
6_-_nF_n; 2≦n≦6, m<n) manufacturing method. 2. Perform the fluorination reaction in the liquid phase at normal pressure or under pressure, from 0 to
The manufacturing method according to claim 1, which is carried out in a temperature range of 200°C. 3. Dihydrohalogenopropanes are 1,1,1,2,2
, 3-hexachloropropane. 4. Dihydrohalogenopropanes are 1,1,2,2,3
, 3-hexachloropropane. 5. Dihydrohalogenopropanes are 1,1,1,2,3
-Pentachloro-2-fluoropropane Claim 1
Or the manufacturing method described in 2. 6. The manufacturing method according to claim 1 or 2, wherein the dihydrohalogenopropane is 1,1,1,3-tetrachloro-2,2-difluoropropane. 7. The manufacturing method according to claim 1 or 2, wherein the dihydrohalogenopropane is 1,1,3,3-tetrachloro-2,2-difluoropropane. 8. The production method according to claim 1 or 2, wherein the dihydrohalogenopropane is 1,1,1-trichloro-2,2,3-trifluoropropane. 9. The manufacturing method according to claim 1 or 2, wherein the dihydrohalogenopropane is 1,1,3-trichloro-1,2,2-trifluoropropane. 10. The production method according to claim 1 or 2, wherein the dihydrohalogenopropane is 1,1,3-trichloro-2,2,3-trifluoropropane.