JPH02117624A - Fluorinating agent - Google Patents

Abstract

PURPOSE:To obtain a novel fluorinating agent for carrying out substitution of chlorine in an organic chlorine compound of fluorine compound or addition of fluorine to an unsaturated compound at a high level of substitution in high yield by using fluorinated indium or indium fluoride. CONSTITUTION:A novel fluorinating agent, obtained by using fluorinated indium or indium fluoride synthesized from indium or an indium compound (e.g., indium chloride, bromide, iodide, carbonate, nitrate or oxide) and used for substitution of chlorine in organic chlorine compounds or fluorides (especially polychlorides or fluorides of lower hydrocarbons, hexachloroacetone, benzotrichloride and derivatives thereof are industrially important) or addition of fluorine to substituted or unsaturated compounds. The substitution of the chlorine or addition of fluorine can be carried out in high yield and compounds can be substituted by the fluorine at a high level.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new fluorinating agent, which replaces chlorine in an organic chlorine compound or fluorine compound with fluorine or adds fluorine to an unsaturated compound. This invention relates to a novel fluorinating agent.

The present invention also relates to a novel fluorinating agent for producing fluorine-containing organic compounds.

[Conventional technology]

Various high-valent metal fluorides, that is, higher-order metal fluorides, are known as fluorinating agents.

Examples include cobalt trifluoride (CoF2), manganese trifluoride (MnF2), silver difluoride (AgF2), or a compound having a composition in which these are mixed with an alkali metal fluoride (for example, K2CoF4).

Fluorination is performed by using these higher metal fluorides to replace fluorine with hydrogen or chlorine in hydrocarbons or chlorinated hydrocarbons.

In addition, low-fluoride metals include silver fluoride (AgF), potassium fluoride (KF), and thallium fluoride (TIF).
, mercury fluoride (HgF, HgF2), and antimony fluoride (SbF 5bF5), etc.
.

Also known as other drugs.

There is no known example in which the indium-containing fluoride of the present invention is used as a fluorination agent.

[Problem to be solved by the invention]

An object of the present invention is to provide a new fluorinating agent for producing a fluorine-containing compound from an organic chlorine compound or a fluorine compound by replacing chlorine with fluorine or adding fluorine to an unsaturated compound.

[Means to solve the problem]

As a method for fluorinating 6-organic chlorine compounds or fluorine compounds, methods using high-valent metal fluorides, halogen fluorides, and low-fluoride metals are known.

Cobalt trifluoride (C
o F s ), silver difluoride (A g F 2 )
, manganese trifluoride (M n F a ), or a mixture of these and an alkali metal fluoride (for example, K Co F 4 ), which reacts with organic compounds in almost the same way as fluorine. gives a highly fluorinated compound. Examples of halogen fluorides include Cfl F, Cil F3. BrF3゜B r F s
etc. are known.

Low-fluoride metals include silver fluoride (AgF), potassium fluoride (KF), thallium fluoride (TIF), mercury fluoride (HgF), and mercury difluoride (HgF 2 ).
Antimony trifluoride (SbF3), antimony pentafluoride (SbF5), etc. are also known. All of these fluorides are manufactured without using elemental fluorine, and the hydrogen in the compound is Although it is rarely replaced with fluorine, it has the ability to replace chlorine and bromine with fluorine, so it is used to produce fluorides using organic compounds containing chlorine and bromine as starting materials. Among these, AgF
.

KF, TIF, and HgF are mainly used for monohalogen compounds, and SbF3 and SbF5 are mainly used for polyhalogen compounds.

Antimony fluoride is also industrially important for fluorocarbon synthesis, and the following rules are said to hold regarding its fluorination ability.

For example, in the case of SbF3, (1) -CCN3 is the most reactive and easily -CF
It becomes 10F20g after passing through CN2, but it is difficult to become CF3.

(11) -CHCII 2 gradually becomes -CHPCI, but hardly becomes -CHF2.

(iii) -CH2CN and -CHCJII- hardly react.

In the case of indium fluoride, which is the fluorinating agent of the present invention, -
It can be understood that it is capable of fluorinating ccu3 to -CF3 and -CI(2CN to -CH2F), and is a practically excellent fluorinating agent.

For example, the production of 1.2.2.2-tetrafluoroethane by fluorination of 1-chloro-2,2,2-trifluoroethane using Co, Mn, Ag as fluorinating agents.
The yield of the latter is less than 10% when using fluoride, but when indium fluoride is used, the yield is extremely high (410
78%). This shows that the fluorine in indium fluoride has a unique effect.

Typical examples of organic chlorine compounds or fluorine compounds and unsaturated compounds referred to in the present invention include carbon tetrachloride, chloroform, methylene chloride, hexachloroethane, pentachloroethane, tetrachloroethane, trichloroethane, octachloropropane. , pentachlorpropane, trichloropropane, tetrachlorethylene, tetrafluoroethylene, trichlorethylene, hexachlorpropene, pentachlorpropene, tetrachloropropene, hexafluoropropene, pentafluoropropene, trifluoropropene, hexachlorobutadiene, hexafluoro Butadiene, benzotrichloride, chlorinated benzotrichloride, ether containing trichloromethyl group, ketone containing trichloromethyl group, ester containing trichloromethyl group, acid halide containing trichloromethyl group, etc., or trichloromethyl group, dichloromethyl group It is a polyhalogenated organic compound in which some of the chlorine atoms are replaced with fluorine atoms.

Among these, those that are industrially important are polychlorinated products of lower hydrocarbons, fluorinated products, hexachloroacetone, benzotrichloride, and derivatives thereof. When the indium fluoride of the present invention is used as a fluorinating agent, a fluorine-containing compound can be produced with high yield and high selectivity. Indium fluoride can be used in the reaction in the form of powder, granules, tablets, etc. It is easier to handle if it is formed into a tablet or the like, but it is not particularly limited to this shape.

Indium fluoride has the corresponding chloride, bromide, iodide, carbonate, nitrate, sulfate, fluorosilicate,
Acetates, oxides or corresponding metal powders, lower fluorides, etc. can be used as fluorides with fluorine. Let us give a concrete example of an indium compound. For example, oxide (■n203.!n203・3H20), hydroxide (In(OH)a), sulfide (In2S3)
, phosphate (In(PO)), k-salt (In2 (S
O4)3゜In2 (S04)3・6H20,In2(
SO4)3・12H20), nitrate (In(N03)3
・3H20), oxalate (I n (CO)
” 6 H20), halides (I n F I
n F3・3H20゜3″ I n CI I n C473φx H20, I
n B r a r3 ゛1+ I n I a), halogen complex salt (M+ I n (
S 04) 2-1+ 4HO,M2 In(SO4) 2"12H20゜1+ M [InCN (HO)), M1+[InBr1
+ 1÷ (HO))M3 (InF6), M3 [1nCffe
).

1+ M (I n B re ), M represents a monovalent cation. ), organic indium compounds (CHI n (O
H) 2) etc. can be mentioned. Other indium compounds include halides, oxides, sulfides, and sulfides such as 1+ InC, 77, InBr, Inl, Ink, and In25, as well as In2+ and In2+.

1nCN, , InBr2. Inl2. Halides such as InS, sulfides, etc. are also known and can be used as long as they are stable.

Indium fluoride may be molded as it is or mixed with a stable compound (for example, calcium fluoride) by a known method such as a tableting method. Further, it may be used by being supported on a stable carrier (for example, aluminum trifluoride, etc.).

In practical use, indium fluoride can be easily produced by treating an indium compound or metal indium with hydrofluoric acid.

When producing the corresponding indium fluoride using fluorine, it is charged into a reactor made of a commonly used corrosion-resistant material and fluorinated with fluorine gas. Fluorine gas is diluted with a gas inert to fluorine, such as nitrogen, helium, or HF.
You can also use

Furthermore, instead of using fluorine gas, a gaseous fluorine compound that easily releases fluorine, such as chlorine trifluoride, may be used.

The following can be cited as a preferable method for producing indium fluoride.

I) After dissolving metallic indium in an acid, for example nitric acid, this solution is impregnated into activated alumina, dried and then calcined in air to form the final indium oxide-alumina. Next, 20
A method of treating indium fluoride-aluminum fluoride with anhydrous hydrofluoric acid in a gas phase at a temperature range of 0 to 400°C.

1i) The same method is used to obtain indium oxide-alumina, but this material is subjected to water X reduction in a gas phase at a temperature range of 200 to 400°C to obtain metallic indium-alumina. Further, this product is treated with anhydrous hydrofluoric acid in a gas phase at a temperature range of 200 to 400°C to obtain indium fluoride-aluminum fluoride.

Metallic indium treated with hydrofluoric acid in the gas phase is also effective.

The raw materials are supplied to a reactor filled with indium fluoride or indium fluoride prepared in this way and allowed to react. In this case, either a flow method or a circulation method may be used, and the reactor may be either a fixed bed or a fluidized bed.

The reaction pressure can be normal pressure, increased pressure, or reduced pressure, but normal pressure systems are easier to operate. The reaction temperature is 100-5
A range of 00°C is suitable. In this temperature range, especially when the conversion rate of the raw material gas does not increase on the low temperature side, it is preferable to use a circulation method. Considering the separation and purification of the target product, by-products that have a boiling point close to that of the raw materials may be produced, so the circulation method is practically preferable.

〔Example〕

Next, the present invention will be explained in more detail by showing Examples and Comparative Examples.

Example 1 Indium fluoride, InFa, was prepared in tablet form (5+n+
sφ x 5 mm), and 172 g of it was packed into a nickel reactor (25 mφ 39.5g of 2-trifluoroethane
, introduced into the reactor by flow method during 6 hours.

The reaction products were collected, weighed, and analyzed for composition by conventional gas chromatography. As a result, the initial performance was as follows.

1-chloro-2,2,2-trifluoroethane conversion rate:
9.9% 1.2,2.2-tetrafluoroethane
Yield: 9.5% Selectivity: 9 [1.0% Example 2 In the same manner as in Example 1, only the reaction temperature was set to 410"C, and 1-chloro-2,2,2-)lifluoroethane was added. When introduced into the reactor, the following results were obtained.

1-chloro-2,2,2-trifluoroethane conversion rate:
112.6% 1.2,2,2-tetrafluoroethane Yield: 78.5% Selectivity: 95.1
% Example 3 250 g of indium chloride, In CD a, was molded into a pellet of 5 dragons φ x 5 dragons, and then filled into the same reactor as in Example 1. Under the following conditions, firstly hydrofluoric acid diluted with nitrogen and finally only hydrofluoric acid was flowed in the gas phase.I n Cj! A was fluorinated.

Hydrofluoric acid concentration = 25-100% Temperature: 200-420°C (SV): 500 hr' (0°C, 1 atm equivalent value) Using this indium fluoride, 1-chloro -2,2,2-trifluoroethane was introduced into the reactor, and 1-chloro-2,2,2-
Conversion rate of trifluoroethane 80.2%, 1.2.2.
The yield of 2-tetrafluoroethane was 76.2%.

Example 4 After molding 145 g of indium oxide, In2O3, into pellets of 5 mm diameter x 5 sizes, the pellets were charged into the same reactor as in Example 1. In the first stage of fluorination, reduction was performed using hydrogen at a temperature in the range of 200 to 420°C. Next, fluorination treatment was performed under the same conditions as in Example 3, and 1-chloro-
When 2,2,2-trifluoroethane was introduced into the reactor, the conversion rate of 1-chloro-2,2,2-trifluoroethane was 79.1%, and the conversion rate of 1.2,2,2-tetrafluoroethane was 79.1%. The yield was 75.0%.

Comparative example 1 Silver fluoride (AgF), cobalt fluoride (CoF3)
Example 2 except using 127 g and llBg, respectively.
Under the same conditions as above, 1-chloro-2,2,2-trifluoroethane was introduced into the reactor. For any fluoride, 1.
The yield of 2,2,2-tetrafluoroethane was less than 10%.

Example 5 Same as Example 1, but reaction temperature 150°C, purity 99
．． 39.8 g of chloroform with a concentration of 5% or more was introduced into the reactor using a flow method.

The reaction products were collected, weighed, and analyzed for composition by conventional gas chromatography. As a result, the initial performance was as follows.

CHCN3 conversion rate: 83.5% CHCl2F yield: 88.6% CHClF2 yield: 12.9% CHF yield: 2.0% Example 6.7 Example 3 except that the reaction temperature was 175.205°C Similarly, CHC,l! 3 was introduced. As a result, the initial performance was as follows.

Temperature C113C13 (℃) Conversion rate [%] Yield CllCfI21' 14.7 Rate [%] CIICRF2CHF3 51.0 34J O100 Examples 8 to 11 Same as Example 1, but the starting materials shown in Table 1 were added to the reactor. It was introduced under the Distribution Act. The reaction conditions and results are also shown in Table 1.
Shown below.

(Margin below) be.

Claims (1)

[Claims] A fluorinating agent for replacing chlorine in an organic chlorine compound or fluorine compound or adding fluorine to an unsaturated compound using indium fluoride or indium fluoride synthesized from indium or an indium compound.