The method of obtaining perftoran ethane or propane range
(57) Abstract:The invention relates to the production of performancenow (halocarbons). Perchlorate interacts with fluorine at elevated temperature in the layer of aluminium-containing catalyst. As raw materials use-hydro--harpercollin, preferably 1-hydro-2-CHLOROTETRAFLUOROETHANE (in pure form or in azeotropic mixture with OCTAFLUOROCYCLOBUTANE) or 1-hydro-3-chlorohexadecane. The process is conducted in two successive reaction zones. In the first zone at 100-300°C using aluminum oxide modified with fluoride of a metal of group IB or VIII, namely fluoride, Nickel or silver, and in the second zone is at 300-400°C With aluminum oxide modified with a fluoride of a metal of group III or V, namely fluoride antimony or aluminum. Crystalline aluminum oxide has a specific surface area of 2-5 m2/g and contains 1-8 wt. % of metal fluoride. On one mole of the organic raw material serves 1.4 to 1.8 mol of fluorine. As a result of increased output of performancenow to 93-97%. 11 C.p. f-crystals, 3 tables. The invention relates to the chemical industry and is intended to receive performancenow, namely freon (Halocarbon 116) or OCTAFLUOROPROPANE (Halocarbon 218), ispolzuyuyuschih liquids in units of the low-temperature type.A method of obtaining perftoran ethane or propane range (freon or OCTAFLUOROPROPANE) by fluorination of halogenoalkane anhydrous hydrogen fluoride in the presence of a catalyst active chromium oxide [U.S. Pat. USA N 3258500, publ. 28.06.66]. The disadvantage of this method is the low yield of the target product, due to the weak effect of soft fluorinating agent is hydrogen fluoride.Know of any other way of getting perftoran, in particular OCTAFLUOROPROPANE that the set of essential characteristics most similar to that proposed. This method consists in processing perchloroethane, such as trichloropentafluoropropane, elementary fluorine at elevated temperature in the catalyst bed, which is used as aluminum TRIFLUORIDE [U.S. Pat. USA N 2831035, publ. 15.04.58]. This method is characterized by higher output perftoran thanks to the use of "hard" fluorinating agent is elemental fluorine.The disadvantage of this method is the increased output of products of destructive fluorination, due to the low catalyst efficiency.The technical problem solved by the present invention, increase of the output of performancenow.As-hydro-chlorphentermine use 1-hydro-2-CHLOROTETRAFLUOROETHANE, which can be taken in the form of an azeotropic mixture with OCTAFLUOROCYCLOBUTANE, or 1-hydro-3-chlorohexadecane.In the first reaction zone using a catalyst NiF2/Al2O3or AgF/Al2O3and maintain a temperature of 100 -300oC.In the second reaction zone using a catalyst SbF5/Al2O3or AlF3/Al2O3and maintain a temperature of 300 ° -400oC.Fluorine is served in the amounts of 1,4 -1,8 mol per 1 mol-hydro--chlorphentermine.The aluminum oxide used in crystalline form with a specific surface area of 2 -5 m2/g and the content of the metal fluoride 1 to 8% by weight of the catalyst.Example 1
The freon was received at the laboratory unit, comprising an electrolytic cell for obtaining fluorine, dosing and feeding on fluoridation of 1-hydro-2-globe the Torah, hydrogen fluoride and chlorine, site dewatering, site of condensation products of fluorination (using liquid air) and low-temperature distillation column for separation of the target product. Each reactor is a cylindrical device made of Nickel with external electric heating.In the first reactor was loaded catalyst NiF2/Al2O360 cm3. The specific surface of the catalyst 3 m2/year the Amount of fluoride Nickel, deposited on the surface of alumina amounted to 8% by weight of the catalyst. In the second reactor was loaded a catalyst comprising a crystalline aluminum oxide modified with PENTAFLUORIDE antimony in the amount of 1.5 wt.%. The specific surface of the catalyst 4.2 m2/,Fluorine was obtained by electrolysis TRIFLUORIDE potassium KF2HF cleaning it from the hydrogen fluoride in the column filled with calcined sodium fluoride, and directed in the first direction of gas flow reactor with a speed of 3.6 l/h There gave 1-hydro-2-harpertrade from the container through the rheometer at a rate of 2.4 l/h Temperature in the first reactor was maintained at 200oC. the Reaction gases from the first reactor was sent to the second reactor, which is maintained tempera is drained digidrirovanny calcium chloride and are condensed at a temperature of - 196oC. Low-temperature rectification products fluorination was conducted on a laboratory column efficiency 40 theoretical plates.The content of the basic substance in the target product, isolated by distillation, more than 99 wt.%. The duration of the process of fluorination was 5 hours. During the experience served on fluoridation 68 g of 1-hydro-2-chlorphentermine. As a result of experience, dedicated, 64 g of freon. Conversion of the original organic materials exceeded 99%, the yield of the target product amounted to 93.1% of.Examples 2-9
Getting freon and OCTAFLUOROPROPANE was performed with the setup described in example 1. Specific conditions and results of experiments are presented in tables 1-3.Examples 10-13 control (with catalyst prototype)
Experiments were performed with the setup described in example 1, but in both reactor was loaded aluminum TRIFLUORIDE. Conditions and results of experiments are also presented in tables 1-3.From the presented data shows that the proposed method is characterized by a high yield of the target products: in optimal conditions, the yield of OCTAFLUOROPROPANE exceeds 97%, the output of freon - 93% (examples 1 and 6). Tables 2 and 3 show that in perlocation (1-chlorphentermine or 1-harpertrophy), and in the second zone at other temperature and the catalyst is selectively substituted by a chlorine atom in the fluorine obtaining the target product. In experiments with catalyst AlF3(by known means) fluoridation-hydro-chlorphentermine characterized by an increased contribution destructive fluorination in the first and in the second reaction zone, which ultimately leads to a significant reduction of the yield of the target product (op. 10-13).The proposed method will allow highly efficient to dispose of by-products in the manufacture of tetrafluoroethylene - -hydro-chlorphentermine. 1. The method of obtaining perftoran ethane or propane series by contacting perchlorate with fluorine at elevated temperature in the layer of aluminium-containing catalyst, characterized in that as the source perchloroethane use-hydro--harperteen, the process is conducted in two successive reaction zones and the catalyst used in the first zone alumina modified with fluoride of a metal from groups IB or USW, and in the second zone - alumina modified with fluoride of a metal of groups SA or UA.2. The method according to p. 1, characterized in that as the m, that as the source of 1-hydro-2-CHLOROTETRAFLUOROETHANE use azeotropic mixture of 1-hydro-2-CHLOROTETRAFLUOROETHANE with OCTAFLUOROCYCLOBUTANE.4. The method according to p. 1, characterized in that the as-hydro--chlorphentermine use 1-hydro-3-chlorohexadecane.5. The method according to p. 1, 2, 3 or 4, characterized in that in the first reaction zone using a catalyst NiF2/Al2O3.6. The method according to p. 1, 2, 3 or 4, characterized in that in the first reaction zone using a catalyst AgF/Al2O3.7. The method according to p. 5 or 6, characterized in that in the first reaction zone to maintain the temperature of 100 - 300oC.8. The method according to p. 1, 2, 3 or 4, characterized in that the second reaction zone using a catalyst SbF5/Al2O3.9. The method according to p. 1, 2, 3 or 4, characterized in that the second reaction zone using a catalyst AlF3/Al2O3.10. The method according to p. 8 or 9, characterized in that the second reaction zone to maintain the temperature of 300 - 400o.11. The method according to p. 1, characterized in that the fluorine serves in the amount of 1.4 to 1.8 mol per 1 mol-hydro--chlorphentermine.12. The method according to p. 1, wherein the eating of fluoride metal 1 - 8% by weight of the catalyst.
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to preparation of alkylaromatic intermediates including perfluorinated carbon atom utilized in production of agrochemically important active compounds. Intermediates simultaneously containing aniline function are obtained from homocyclic arylcarbamoyl fluoride including at least one perhalogenated carbon atom preferably bearing at least two halogen atoms capable of being replaced by fluorine atoms when in liquid-phase contact with hydrofluoric acid and water. During this reaction, molar ratio of hydrofluoric acid to arylcarbamoyl fluoride is maintained equal to 4, preferably to 5 and not higher than 11. Water is added to reaction mixture (at 10 to 90°C) when only one exchangeable halogen atom remains unreplaced. Arylcarbamoyl fluoride is obtained in situ by adding corresponding isocyanate to liquid hydrofluoric acid at temperature not exceeding 10°C. Process is carried out continuously in two reactors, the first one serving for halogen exchange reaction and the second for addition of water. Temperature 40°C is maintained until only one exchangeable halogen atom remains unreplaced.
EFFECT: increased yield and improved quality of desired product and economical characteristics.
9 cl, 4 ex