JPH02207041A - Production of fluoropropanes and chlorofluoropropanes having difluoromethylene group - Google Patents

Abstract

PURPOSE:To obtain the subject compounds in a high yield by consecutively fluorinating chlorines of a chlorofluoropropane having a difluoromethylene group using a fluorinating agent containing a specified metallic element such as manganese. CONSTITUTION:A compound of formula I (0<=m<=5) having a difluoromethylene group is fluorinated by a fluorinating agent such as a fluoride, a fluoride halide or an oxide fluoride containing one or more elements selected from Mn, Ag, Sb, Ta, Nb, Ce, Co, Al, Cr, Mg, Ca, Ba, Zn, Si, Li, Na, K, Cs and Rb to selectively produce the objective compound of formula II (1<=n<=6; m<n) having a difluoromethylene group and useful as an etching agent, etc., for production of electronic components and an intermediate for synthesis of hydrogen- containing fluons. In addition, when (a) KF or CsF or (b) SbF3, SbF3Cl2 or SbF5 is used as the fluorinating agent, a phase-transfer catalyst and either of and SbCl5 are added thereto respectively in (a) and (b).

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to fluoropropanes and chlorofluoropropanes (C3Ct a-
nF2. . ;1≦n≦6).

Fluoropropanes having a difluoromethylene group are useful as etching agents for manufacturing electronic parts, and chlorofluoropropanes are useful as intermediates for the synthesis of hydrogen-containing fluorocarbons that do not destroy the ozone layer in the rVI zone.

[Prior art and problems to be solved by the invention] Conventionally, as a synthetic route for fluoropropanes and chlorofluoropropanes having a difluoromethylene group, 1゜1-dichloro-2,2-difluoropropanes are synthesized in the presence of aluminum chloride. A synthesis method is known in which ethylene or ethylene having a difluoromethylene unit such as 1-chloro-1,2,2-trifluoroethylene is added with dichlorodifluoromethane, trichlorofluoromethane, or the like. However, these methods produce reaction by-products that have methylene groups other than difluoromethylene and have similar boiling points to the target product, so multiple purification steps are required to obtain a highly pure product. It has the disadvantage of being

[Means for Solving the Problems] The present inventor has developed fluoropropanes and chlorofluoropropanes (CaC16-
As a result of intensive research into efficient production methods for oF2-; 1≦n≦6, man), we found that chlorofluoropropanes having a difluoromethylene group (C3Ct 6-F
2-; O≦m≦5) is Mn, Ag.

Sb, Ta, Nb, Ce, Co,
Al, Cr.

Mg, Ca, Ba, Zn, Si,
Li, Na.

By fluorination with a fluorinating agent consisting of a fluoride, fluorohalide or fluoride oxide containing at least one element selected from the group consisting of K, Cs and Rb, the ratio of the fluorinating agent to the starting material can be adjusted. Fluoropropanes and chlorofluoropropanes having a difluoromethylene group by sequentially replacing chlorine with fluorine according to the
(C3C1s-nF2”n: 1≦n≦6, man)
The present invention has been provided based on this discovery.

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

That is, when chlorofluoropropanes having a difluoromethylene group (C3Cte-F2-; 0sm≦5) are fluorinated with the above fluorinating agent, fluoropropanes having a difluoromethylene group and chlorofluoropropanes have a difluoromethylene group as shown in the following formula. Propanes (C3Ct6-, IF
2. It was found that n; 1≦n≦6, m<n) was produced in good yield.

Fluorinating agent C3Ci 6--F 2-- ” C3Ct
6-nF 2◆-0≦m≦51≦n≦6 m<n In this reaction, Mn, Ag, Sb, T
a.

Nb, Ce, Co, AI, Cr,
Mg, Ca.

A fluorinating agent consisting of a fluoride, a fluorohalide, or a fluoride oxide containing at least one element selected from the group consisting of Ba, Zn, St, Li, Na, K, Cs, and Rb can be used.

Specifically, MnFt, AgF, AgF2, and SbFa.

5bFxCE2, 5bFs, TaF5. NbF
s, CaFt, C0F3. AlC1F2.
CrO2F2. LiF, NaF,
KF, CsF, RbF,
KF-MgF2. KF CaFt, KF
BaF2. ZnF2゜S i Fa and Na
Examples include 5iFs.

Chlorofluoropropanes having a difluoromethylene group (C3Cl e-F 2-; 0≦m≦5) used as raw materials
) as l, 1.1.3.3.3-hexachloro-2°2-difluoropropane (R-212ca),
1,1゜1,. 3.3-pentachloro-2,2,3-trifluoropropane (R-213ca), 1.1.3
．． 3-tetrachloro-1゜2,2,3-tetrafluoropropane (R-214ca), 1.1.1.3-tetrachloro-2,2,3,3-tetrafluoropropane (
R-214cb), 1,1.3-trichloro-1,2,
2,3,3-pentafluoropropane (R-215ca
), i, 1.1-trichloro-2,2,3,3,3
-Pentafluoropropane (R-215cb), 1,3
-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca), 1,1-dichloro-1,
2,2,3,3,3-hexafluoropropane (R-2
16cb), 1-chloro-1,1,2,2,3,3
, 3-heptafluoropropane (R-217ca), all of which are known compounds.

The amount of fluorinating agent used in the fluorination reaction is not particularly limited. It is preferable to use a fluorinating agent in a stoichiometric amount based on the number of chlorine to be replaced in the starting material, but it is preferable to use a fluorinating agent in a stoichiometric amount based on the number of chlorine to be replaced in the starting material. In order to react with
Double the molar amount or more may be used.The fluorinating agent after the reaction is recovered as chloride or chloride oxide, but these can also be regenerated with hydrogen fluoride or fluorine gas. be. The conditions for the fluorination reaction vary depending on the fluorinating agent used, but are usually 0 to 450°C, particularly 50 to 3°C.
A reaction temperature of 0.000C is preferred.

Although the reaction can be carried out without a solvent, it is preferable to use a fluorinating agent. Protic polar solvents include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, hexamethylphosportriamide, N-methyl-2-pyrrolidone, acetonitrile, benzonitrile, nitromethane, Examples include dioxane, diglyme, tetraglyme, and acetone.

In particular, when an alkali metal fluoride such as KF or CsF is used as a fluorinating agent, sulfolane, N, N-dimethylformamide is preferable. A phase transfer catalyst may be added as a reaction promoter. Such a phase transfer catalyst Examples include quaternary ammonium salts such as tetramethylammonium chloride and tetrabutylammonium bromide, quaternary phosphonium salts such as tetrabutylphosphonium bromide and tetraphenylphosphonium bromide, and crown ethers. The amount of phase transfer catalyst added is usually 0.01 to 10% relative to the alkali metal fluoride.
0ffl amount%, especially 0.1 to 30% weight is preferable,
S b F3. as a fluorinating agent. S bF3C12
Alternatively, when using 5bFs, 5bCt3 or SbCls may be added as a catalyst, sbClg or Sb
The amount of Cls added is usually 0.01 to 100jfU, preferably 0.1 to 20% by weight, based on SbF3゜5bF3Ck2 or 5bFs. Chlorofluoropropanes (C3
Cl 6-oF 24n; 1≦n≦6, m<n), 1.1.1.3.3-pentachloro-2,2,3-
) Rifluoropropane (R-213ca), 1.1,3
．． 3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca), 1.1.1.3-tetrachloro-2,2,3,3-tetrafluoropropane (R
-214cb), ■, 1°3-trichloro-1,2,2
,3,3-pentafluoropropane (R-215ca)
, 1.1.1-trichloro-2,2,3°3.3-pentafluoropropane (R-215cb), 1.3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca), 1,1-dichloro-1,2
,2,3゜3.3-hexafluoropropane (R, -2
16cb), 1-chloro-1,1,2,2,3,3,3
-heptafluoropropane (R-217ca) and octafluoropropane (R-218), which can be separated by ordinary operations such as distillation.

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

Example 1 A Hastelloy C autoclave with an internal volume of IQ was charged with 1,1.3.3.3-hexachloro-2 as a starting material.
゜2-difluoropropane (R-212ca) 50g,
90 g of spray-dried potassium fluoride, 9 g of TeI-butylphosphonium bromide, and 480 g of sulfolane were charged, and the mixture was reacted at 200° C. for 10 hours with vigorous stirring.

After cooling, the inorganic salt was removed and the reaction product was analyzed by gas chromatography and NMR. Results 1.1.
1.3.3-pentachloro-2゜2,3-trifluoropropane (R-213ca), 1,1.3.3-tetrachloro-1,2,2,3-tetrafluoro10pane (
R-214ca), 1.1.1.3-tetrachloro-2
, 2,3,3-tetrafluoropropane (R-214c
b), l, 1.3-tric o o-,1,2,2,
,3,3-pentafluoropropane (R-215ca)
, 1.1.1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb), 1.3-dichloro-1,1,2,2,3,3-hexafluoropropane ( R-216ca), ■, 1-dichloro 1.2.2
．． 3.3.3-hexafluoropropane (R-216c
b) It was confirmed that 1-rioo-1,1,2,2,3,3,3-heptafluoropropane (R-217ca) and octafluoropropane (R-218>) were produced.Main results are shown in Table 1.

Example 2 As starting material l, 1.1.3.3-pentachloro-
2,2゜3-trifluoropropane (R-213ca)
A fluorination reaction was carried out in the same manner as in Example 1 except that the reaction product was analyzed. The results are shown in Table 2.

Table 1 Table 2 Example 3 1.1.3.3-tetrachloro-1,2 as starting material
,2゜3-tetrafluoropropane (R-214ca)
A fluorination reaction was carried out in the same manner as in Example 1 except that 50 g of spray-dried potassium fluoride, 70 g of spray-dried potassium fluoride, and 7 g of tetrabutylphosphonium bromide were used, and the reaction products were analyzed. The results are shown in Table 3.

Table 3 Example 4 1.1.1.3-tetrachloro-2,2 as starting material
,3゜3-tetrafluoropropane (R-214cb)
A fluorination reaction was carried out in the same manner as in Example 3 except that the reaction product was analyzed. The results are shown in Table 4.

Table 4 Example 5 1.1.3-trichloro-1,2,2 as starting material
,3,3-pentafluoropropane (R-215ca)
A fluorination reaction was carried out in the same manner as in Example 1 except that 50 g of spray-dried potassium fluoride, 55 g of spray-dried potassium fluoride, and 6 g of tetrabutylphosphonium bromide were used, and the reaction product was analyzed. The results are shown in Table 5.

Table 5 Example 6 Starting material: l, 1,1-trichloro-2,2,3
,3,3-pentafluoropropane (R-215cb)
A fluorination reaction was carried out in the same manner as in Example 5 except that the reaction product was analyzed. The results are shown in Table 6.

Example 7 1,3-dichloro-1,1,2,2,3 as starting material
, 3-hexafluoropropane (R-216ca) 5°
A fluorination reaction was carried out in the same manner as in Example 1, except that Og, 40 g of spray-dried potassium fluoride, and 4 g of tetrabutylphosphonium bromide were used, and the reaction products were analyzed. The results are shown in Table 7.

Table 7 Example 8 1,1-dichloro-1,2,2,3,3 as starting material
, 3-hexafluoropropane (R-216cb) was used, but the fluorination reaction was carried out in the same manner as in Example 7, and the reaction product was analyzed. The results are shown in Table 8.

Table 8 Example 9 1-4-row 1.1.2.2.3.3.
3-heptafluoropropane (R-217ca) 50g
A fluorination reaction was carried out in the same manner as in Example 1 except that 55 g of cesium fluoride and 6 g of tetrabutylammonium bromide were used, and the reaction temperature was 150° C., and the reaction product was analyzed. The results are shown in Table 9.

Table 9 Example 10 1.1.1-) Rechloro 2.2.3.3 as a starting material in a Hastelloy C autoclave with an internal volume of 20 OmI
゜3-pentafluoropropane (R-215cb) 15
0g of antimony trifluoride and 60g of antimony trifluoride were charged, and the mixture was reacted at 150'C for 10 hours with vigorous stirring.

After cooling, the inorganic salt was filtered out, and the crude reaction solution was washed with water and dried, and the reaction product was analyzed by gas chromatography and NMR. The results are shown in Table 10.

Table 10 Example 11 1.1.1-Trichloro-2,2,3,
3゜3-pentafluoropropane (R-215cb) 1
50 g of antimony trifluoride, 60 g of antimony trifluoride, and 3 g of antimony trichloride were charged, and the mixture was reacted at 150° C. for 10 hours with vigorous stirring. After cooling, the inorganic salt was filtered out, and the crude reaction solution was washed with water and dried, and the reaction product was analyzed by gas chromatography and NMR. The results are shown in Table 11.

Table 11 After the reaction crude liquid was washed with water and dried, the reaction product was analyzed by gas chromatography and NMR. Table 12 shows the results.
Shown below.

Table 12 Example 12 In a Hastelloy C autoclave with an internal volume of 200 ral, i, 1.1-trichloro-2,2,
3,3゜3-pentafluoropropane (R-215cb
), 60 g of antimony trifluoride, and 3 g of antimony pentachloride.
Allowed time to react. After cooling, the inorganic salt was separated into a furnace, and Example 1
3. After adding 60 g of antimony trifluoride to a Hastelloy C autoclave having an internal capacity of 200 ml, 23 g of chlorine gas was introduced to prepare antimony fluoride. After crushing the resulting thin film of di-chemically engineered antimony fluoride, use K as the starting material.
．． 3-pentafluoropropane (R-215cb) 15
0 g was charged and reacted at 150° C. for 10 hours with vigorous stirring. After cooling, the inorganic salt was filtered out, and the crude reaction solution was washed with water and dried, and the reaction product was analyzed by gas chromatography and NMR. The results are shown in Table 13.

Table 13 Table 14 Example 14 Contents: 1.1.1-trichloro-2,2,3 was added as a starting material to a 200 ml Hastelloy C autoclave.
,3゜3-pentafluoropropane (R--215cb
) and 80 g of antimony pentafluoride were charged and reacted at 150° C. for 10 hours with vigorous stirring.

After cooling, the inorganic salt was removed, and the crude solution of the first reaction was washed with water and dried, and the reaction product was analyzed by gas chromatography and NMR. The results are shown in Table 14.

[Effects of the Invention] The present invention provides that fluoropropanes and chlorofluoropropanes having difluoromethylene groups can be selectively produced by reacting chlorofluoropropanes having difluoromethylene groups with a fluorinating agent as raw materials. have an effect.

Claims (1)

[Claims] 1. Chlorofluoropropanes having a difluoromethylene group (C_3Cl_6_−_mF_2_+_m; 0≦
m≦5) for Mn, Ag, Sb, Ta, Nb, Ce, Co
, Al, Cr, Mg, Ca, Ba, Zn, Si, Li,
It has a difluoromethylene group that is fluorinated with a fluorinating agent consisting of a fluoride, a fluorinated halide, or a fluoride oxide containing at least one element selected from the group consisting of Na, K, Cs, and Rb. Fluoropropanes and chlorofluoropropanes (C
_3Cl_6_-_nF_2_+_n; 1≦n≦6, m
<n) Manufacturing method. 2. The manufacturing method according to claim 1, wherein the fluorinating agent is KF or CsF. 3. Claim 1 in which a phase transfer catalyst is used during the fluorination reaction.
and the manufacturing method described in 2. 4. Claims 1 to 3 in which a quaternary ammonium salt or a quaternary phosphonium salt is used as a phase transfer catalyst during the fluorination reaction.
The manufacturing method described in. 5. The manufacturing method according to claim 1, wherein the fluorinating agent is SbF_3, SbF_3Cl_2 or SbF_5. 6. The manufacturing method according to claims 1 to 5, wherein SbCl_3 or SbCl_5 is used as the catalyst. 7. Chlorofluoropropanes having a difluoromethylene group are 1,1,1,3,3,3-hexachloro-2,
The manufacturing method according to claims 1 to 6, which is 2-difluoropropane. 8. Chlorofluoropropanes having a difluoromethylene group are 1,1,1,3,3-pentachloro-2,2,
The manufacturing method according to claims 1 to 6, which is 3-trifluoropropane. 9. Chlorofluoropropanes having a difluoromethylene group are 1,1,3,3-tetrachloro-1,2,2,
The manufacturing method according to any one of claims 1 to 6, wherein 3-tetrafluoropropane is used. 10. Chlorofluoropropanes having a difluoromethylene group are 1,1,1,3-tetrachloro-2,2,3
, 3-tetrafluoropropane. 11. Chlorofluoropropanes having a difluoromethylene group are 1,1,3-trichloro-1,2,2,3,
The manufacturing method according to claims 1 to 6, which is 3-pentafluoropropane. 12. Chlorofluoropropanes having a difluoromethylene group are 1,1,1-trichloro-2,2,3,3,
The manufacturing method according to claims 1 to 6, which is 3-pentafluoropropane. 13. Chlorofluoropropanes having a difluoromethylene group are 1,3-dichloro-1,1,2,2,3,3
-Hexafluoropropane, the manufacturing method according to claims 1 to 6. 14. Chlorofluoropropanes having a difluoromethylene group are 1,1-dichloro-1,2,2,3,3,3
-Hexafluoropropane, the manufacturing method according to claims 1 to 6. 15. Chlorofluoropropanes having a difluoromethylene group are 1-chloro-1,1,2,2,3,3,3-
The manufacturing method according to claims 1 to 6, which is heptafluoropropane.