Methods of obtaining 1,1,1,3,3-pentafluoropropane, a way of producing 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane, a way of producing 1,1,1,2,3,3-hexachloropropene, a way of producing 1,1,1,3,3-pendaftar-2,3-dichloropropane

 

(57) Abstract:

In the invention disclosed is a method of obtaining 1,1,1,3,3-pentafluoropropane, namely, that 1,1,1,3,3-pendaftar-2,3-dichloropropan subjected to reaction with hydrogen fluoride in the presence of a catalyst based on a noble metal; a method of obtaining 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane, namely, that halogenated propene General formula (1) foryouth using fluoride in the presence of trihalogen antimony and/or pentavalent antimony in the liquid phase, where the amount of fluoride in 5 times higher than the number of trihalogen antimony and/or pentavalent antimony molar ratio; and method for producing 1,1,1,2,3,3-hexachloropropene, namely, that 1,1,1,2,2,3,3-Heptafluoropropane subjected to reaction with an aqueous solution of alkali metal hydroxide in the presence of a phase transfer catalyst. Thus, revealed a highly effective method for industrial preparation of the desired product in high yield and with low economic cost. 7 C. and 13 C.p. f-crystals, 2 tab.

The invention relates to a method for producing 1,1,1,3,3-pentafluoropropane, which can be used as a substitute for CFC and HCFC used the ve urethane hatebreeder funds. In addition, the invention relates to a method for producing 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane, which may represent an intermediate compound in the synthesis of 1,1,1,3,3-pentafluoropropane, as well as to a method for producing 1,1,1,2,3,3-hexachloropropene.

In patent WO 92/12113 describes the hydrogenolysis of perchloromethane formula CnHmFpXqwhere X represents Cl or Br. Hydrogenolysis are in the gas phase at elevated temperature in the presence of a catalyst-metal group Pd or Pt supported on carbon.

The method of obtaining 1,1,1,3,3-pentafluoropropane using a redox reaction with hydrogen, where the source material is used 1,2,2-trichloropentafluoropropane known (U.S. patent N 2942036).

However, due to low output and producing 2-chlorphentermine and 1,1,3,3,3-pentafluoropropane that are not adequately recovered, this reaction cannot be used for industrial purposes.

On the other hand, 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane itself can be used as an intermediate compound to obtain drugs or agrochemicals, as well as a valuable industrial material, which is alzhemed as refrigerants, blowing agents or cleaning agents, and which by dehydrochlorinating can be entered in the monomers of different types of resins. In particular, 1,1,1,3,3-pendaftar-2,3-dichloropropan can be used as starting material for making 1,1,1,3,3-pentafluoropropane.

Currently, specialists known method of fluorination of propargylamine using HF in the liquid phase in the presence of an antimony halide. For example, E. T. Mcvee etc. received 1,1,1,3,3-pendaftar-2,3-dichloropropan by fluorination of 1,1,1-Cryptor-2,3,3-trichlorpropane using H in the presence of antimonic catalyst (J. Am. Chem. Soc., 70, 2023, (1948)).

However, as 1,1,1-Cryptor-2,3,3-trichlorpropane, H and antimony catalyst come into the reactor immediately before the reaction, this reaction requires not only a high temperature (250oC), but also has a low output 1,1,1,3,3-pendaftar-2,3-dichloropropane up to 50%, resulting in this reaction cannot be used for industrial purposes.

In addition, 1,1,1,2,3,3-hexachloropropene can be used as an intermediate compound for various pharmaceuticals or agrochemicals, as well as the original connection . the particular, this connection can be used as a starting material to obtain 1,1,1,3,3-pendaftar-2,3-dichloropropane (HCFC 225 da).

Generally speaking, 1,1,1,2,3,3-hexachloropropene can be synthesized by dehydrochlorinating 1,1,1,2,2,3,3 - Heptafluoropropane. 1,1,1,2,2,3,3-Heptafluoropropane is a cost-effective source material, which can be easily synthesized from such economically profitable industrial materials, such as chloroform and trichloroethylene.

Known up to the present time the method of synthesis 1,1,1,2,3,3-hexachloropropene is the dehydrochlorination 1,1,1,2,2,3,3-Heptafluoropropane using alkali metal hydroxide, such as KOH in ethanol solvent (J. Am. Chem. Soc., 63, 1438, (1941)).

However, due to the use of alcohol as the reaction solvent, this method requires a filter produced in the reaction of alkali metal chloride, followed by separation of the resulting product from ethanol by distillation.

In addition, it is known that the 1,1,1,2,3,3-hexachloropropene can be obtained from 1,1,1,2,2,3,3-Heptafluoropropane by passing it through a reaction vessel, heated to approximately 400oC, however, takanaga vessel are absolutely necessary because production in the reaction of HCl.

The first aim of the invention is to develop a method of producing 1,1,1,, 3,3-pentafluoropropane (HFC 245 d: (a) with a sufficiently high degree of selectivity, which lacks the above-mentioned disadvantages.

The second objective of the invention to provide an industrial method of producing 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane that does not have the disadvantages of the existing methods mentioned above, and with which 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane (in particular, HCFC 225 da) can be easily produced at minimum cost and with high yield.

The third aim of the invention is to solve the problems associated with the use of the above-mentioned known methods, and the development of cost effective and easily implemented by the industrial method of producing 1,1,1,2,3,3-hexachloropropene.

To solve the problems associated with the use of the above-mentioned known method of producing 1,1,1,3,3-pentafluoropropane, the authors of the present invention conducted a thorough investigation, during which it was determined that the specified target is a product with high output can be obtained by using a redox reaction carried out using hydrogen catalytic the AI of the catalyst based on a noble metal, such as palladium, in the gas phase, resulting in the authors had developed the first invention.

Thus, the first invention relates to a method for producing 1,1,1,3,3-pentafluoropropane with a high degree of selectivity constituting not less than 80% by hydrogen reduction reaction of conducted using 1,1,1,3,3-pendaftar-2,3-dichloropropane as a starting material in the gas-phase system in the presence of a catalyst based on a noble metal such as palladium, and at a temperature of from 30 to 450oC.

In this invention especially important is the fact that hydrogen reduction is performed with the use of a catalyst based on a noble metal in the gas phase. For these purposes may be used in gas-phase reaction with a fixed catalyst bed, the gas reaction fluidized bed of catalyst, etc.

In the specified catalyst in the noble metal can be used palladium, platinum, etc., but from the viewpoint of the selectivity of the reaction, i.e., from the point of view of minimizing the resulting byproduct, palladium is preferred. While it is desirable that me titanium, Zirconia, etc.

The diameter of the particles of the specified media is generally not critical for the reaction, however, the preferred diameter is 0.1 - 100 mm

The concentration of the medium may vary within wide limits, for example from 0.05 to 10% (by weight), however, the preferred concentration is from 0.5 to 5%.

The reaction temperature is generally from 30 to 450oC, and preferably 70 to 400oC.

In the reduction reaction of 1,1,1,3,3-pendaftar-2,3-dichloropropane hydrogen ratio of hydrogen to the source material can vary widely. However, for the specified reaction hydrogenation mainly use at least a stoichiometric amount of hydrogen. This hydrogen can be used in excess of the stoichiometric amount, for example in the amount of 8 mol or more relative to the total pray your source material.

The reaction pressure does not play a decisive role, and this reaction can be carried out with increased, decreased, or normal pressure, but because of the difficulties associated with the use of equipment operating at reduced pressure, this RSET from 0.1 to 300 s, in particular from 1 to 30 C.

The source material, namely 1,1,1,3,3-pendaftar-2,3-dichloropropan is a known compound and can be obtained through the reaction of fluorination of 1,1,1-Cryptor-2,3,3-trichlorpropane (I.e. So Mcvee, ANTHONY TRUCHAN & R. O. BOL T, J. Amer. Chem. Soc., vol. 70, 2023-2024 (1948)).

In addition, to solve the above problems associated with the method of producing 1,1,1,3,3-pentafluoropropane, the inventors have conducted careful studies, which have found that the specified target is a product with high output can be obtained by reduction reaction of hydrogen with the use of 1,1,1,3,3-pendaftar-2,3-dichloropropane as source material, carried out in the gas phase in the presence of a catalyst, in which at least one of the elements added to palladium, which are selected from zirconium and vanadium, and the result of these studies, we developed the second invention.

Thus, the second invention relates to a method for producing 1,1,1,3,3-pentafluoropropane high yield, comprising not less than 80% through a reduction reaction of hydrogen is carried out in the gas system at a temperature of from 30 to 450oC using as source material obavljenih to palladium, choose from zirconium and vanadium.

In the mentioned second invention especially important is the fact that the reaction of the reduction with hydrogen is carried out in a gas-phase system in the presence of a catalyst based on palladium, to which is added at least one element selected from zirconium and vanadium. For these purposes may be used in gas-phase reaction system with a fixed catalyst bed, gas-phase reaction with a fluidized bed of catalyst, etc.

The amount of zirconium and/or vanadium added to palladium, mainly is from 0.01 to 4, and preferably 0.1 to 2 molar ratio.

While it is desirable that the catalyst, which is added at least one element selected from zirconium and vanadium was deposited on at least one carrier selected from activated carbon, silica gel, titanium dioxide, zirconium dioxide, etc.

In this case, the above-mentioned metal, applied to the specified device, can be used in the form of salts, nitrate, oxide, salt, oxide, chloride, etc.

The particle size of the specified media is generally not critical for the reaction, but preferably, if the, for example from 0.05 to 10%, but the preferred concentration is from 0.5 to 5%.

The reaction temperature is generally from 30 to 450oC, and preferably 70 to 400oC.

In the reduction reaction of 1,1,1,3,3-pendaftar-2,3-dichloropropane using hydrogen ratio of hydrogen to the source material can vary widely. However, for the specified reaction hydrogenation typically use at least a stoichiometric amount of hydrogen. This hydrogen can be used in excess of the stoichiometric amount, for example in quantities of 8 moles or more relative to the total pray the source material.

The reaction pressure does not play a decisive role, and this reaction can be carried out with increased, decreased, or normal pressure, but because of the difficulties associated with the use of equipment operating under reduced pressure, the reaction is preferably carried out at elevated or normal pressure.

The reaction time is usually from 0.1 to 300, in particular from 1 to 30 C.

In addition, to solve the above problems, the authors of this application has been developed a method of obtaining 1,1,1,3,3-pins is opened, having a General formula

< / BR>
(provided that in this General formula, X and Y are Cl or F, respectively) (e.g., 1,1,1,2,3,3-hexachloropropene), is subjected to a fluorination reaction using hydrogen fluoride (HF) in the presence of trihalogen antimony and/or pentavalent antimony in the liquid phase, and in the specified reaction system, the amount of fluoride in 5 times or more larger than the number of trihalogen antimony and/or pentavalent antimony molar ratio. This method was the basis of the third invention.

Thus, the third invention relates to the production of 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane by fluorination of propanganda General formula (1) with HF in the presence of fluorinated/chlorinated antimony, namely trihalogen antimony.

Since it is known that chloride of antimony added to the reaction system in which HF is present, is subjected to partial fluorination with education SbClxFy(x + y = 5), while the development of the third invention of the authors of this invention, it was found that if the chloride of antimony used as a catalyst for fluorination of compounds containing hydrogen or dvojno more fluorine, the faster the reaction of fluorination, which contributes to the inhibition of formation of chlorinated product, which is a byproduct of this reaction.

In addition, it was found that due to the presence of HF, the amount of which is excessive in relation to the number of added trihalogen antimony and/or pentavalent antimony, fluoride in trichloride antimony and/or pentachloride antimony can be maintained at a sufficient high level, resulting in a reaction accession will contribute to the selective synthesis of 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane. This fact was also the basis of the third invention.

The number of HF fed to the reactor is consumed quantity of HF plus the amount that is carried away by the resulting product. Thus, the amount of HF in the reaction system remains constant. But if you can keep the excessive levels of HF in the reaction system within the valid ranges of the reactor vessel, then such deviations in quantities of HF is quite permissible. In addition, all the required amount of HF may also be introduced into the reactor before the reaction.

With the th less than the feed speed of fluorinated/chlorinated antimony added to the system, but the smaller feed rate is undesirable due to the reduction of the produced product in relation to the capacity of the reactor.

However, if the amount is too large, the content of fluorine in the fluorinated/chlorinated antimony is reduced, resulting in lower selectivity of the ongoing reaction. Thus, the ratio of the feed rate (mol/h) of propargylamine downloaded (mol/h) of fluorinated/chlorinated antimony generally does not exceed 100 and should not be less than 2. While it is preferable that the amount (mol) of propargylamine supplied for one hour, exceeded the amount (mol) of fluorinated/chlorinated antimony supplied for one hour, not more than 50 times and not less than 5 times.

If the reaction temperature is 40oC or higher, the reaction rate increases, but in this case, if the amount of propanganda in relation to the loaded amount of fluorinated/chlorinated antimony decreases, the selectivity of the reaction decreases.

From the point of view of productivity and high selectivity of the reaction temperature is prepost is ECU to maintain a high reaction pressure is necessary to use expensive equipment, it is desirable that the reaction temperature ranged from 50 to 150oC.

The reaction pressure is increased in accordance with the reaction temperature, however, for the separation of HF and product adequate pressure can be selected in the range from 3 to 30 kg/cm2. Thus, the target compound with high yield can be obtained through the reaction carried out at constant pressure by slowly added to the reaction system propanganda as the starting material and hydrogen fluoride with subsequent selection produced 1,1,1,3,3 - pendaftar-2 - halogeno-3-chloropropane.

The increase in the number of HF with the audience a number of fluorinated/chlorinated antimony in the reaction system does not affect the selectivity of the reaction, but reduces the productivity of the reactor in relation to its capacity. If you use small amounts of HF, despite the progress of the reaction the amount of propanganda must be small in order to avoid the decrease in selectivity. In practice, when carrying out the reaction of hydrogen fluoride to exceed the amount of fluorinated/chlorinated antimony (in molar ratio) 5 times or more, and predpokladanou antimony (in molar ratio) of 50 or more times to 200 times or less.

Also used in the third invention of trihalogen antimony and pentavalent antimony are a mixture of SbF3and SbCl5, SbF3with AbCl2F3partially chlorinated Cl2etc.

In addition to solving the above problems, the authors of this application it was found that the dehydrochlorination of Heptafluoropropane can be accelerated in moderate reaction conditions by conducting the reaction 1,1,1,2,2,3,3-Heptafluoropropane with an aqueous solution of alkali metal hydroxide in the presence of a suitable catalyst phase transfer. This method was the basis of the fourth invention.

Thus, the fourth invention relates to a method for producing 1,1,1,2,3,3-hexachloropropene, namely, that 1,1,1,2,2,3,3-Heptafluoropropane subjected to reaction with an aqueous solution of alkali metal hydroxide in the presence of a catalyst phase transfer.

Generally speaking, the ionic compound, such as alkali metal hydroxide is insoluble in Heptafluoropropane. So this reaction is usually carried out using a suitable solvent, such as alcohol. However, this method predusmatrivaetsya reaction can be carried out using an aqueous solution of alkali metal hydroxide in a two-phase system, however, in this case, the reaction proceeds so slowly that it is often necessary to use relatively harsh conditions in the two-phase system.

However, in accordance with the fourth invention of the authors of this application it was found that the reaction is carried out using an aqueous solution of alkali metal hydroxide in a two-phase system in the presence of a catalyst phase transfer, in particular tetraalkylammonium salt or tetraalkylammonium salt, proceeds quite rapidly under mild conditions.

As cation tetraalkylammonium salt in this reaction can be used benzyltriethylammonium, trioctylamine, tricaprylate, tetrabutylammonium, etc.

As the cation tetraalkylammonium salt in this reaction can be used tetrabutylphosphonium, dioctyladipate etc.

The anion part of the salt along with the above cation can be almost anything, but mostly use the chloride ion and ion bisulfate.

However, the above examples of the catalysts are given only for illustrative purposes and, if necessary, can be used and other types kabit used NaOH, KOH, etc., the concentration of the aqueous solution of alkali metal hydroxide has no hard limits, but preferably, if it is from 5 to 50%, and more preferably from 20 to 40% for the reaction.

These aqueous solutions can be reused after removal produced the alkali metal chloride by sedimentation, filtration or similar and re-add the hydroxide of an alkali metal.

For easier selection of the target crude product 1,1,1,2,3,3-hexachloropropene by separation of the phases, this reaction is performed in a biphasic system. This crude product can be easily purified by distillation, and the used catalyst and unreacted Heptafluoropropane can be restored.

The above reaction is mainly carried out at a temperature in the range from room temperature to 80oC, and preferably from 40 to 60oC.

1,1,1,2,2,3,3-Heptafluoropropane used as starting material may be obtained by reaction of tetrachloroethylene with chloroform in the presence of a catalyst based on a Lewis acid such as aluminium chloride (see patent Opening N 118333/1986 and so on).

About the people, described above for each of the inventions can be used as follows.

First, 1,1,1,2,3,3-hexachloropropene obtained by the method of the fourth invention may be used as starting material for making 1,1,1,3,3-pendaftar-2,3-dichloropropane in accordance with the method of the third invention, and then the specified 1,1,1,3,3-pendaftar-2,3-dichloropropan, in turn, can be used to produce 1,1,1,3,3-pentafluoropropane in accordance with the method of the first or second invention. All these stages allow to obtain the target compound with high yield using efficient methods and inexpensive starting materials.

When 1,1,1,2,3,3-hexachloropropene obtained by the method of the fourth invention may be used to produce 1,1,1,3,3-pendaftar-2,3-dichloropropane in accordance with the method of the third invention, it can also be identified as a product. This method has the advantage that the resulting product can be used as intermediate compounds for obtaining drugs or agrochemicals or it can be used as an intermediate monomer for resins.

The possibility of using the invention in the industry.

Since in accordance with the first and second inventions, the reaction of reduction with hydrogen, in which the source material is 1,1,1,3,3-pendaftar-2,3-dichloropropan, is carried out in the presence of a catalyst based on a noble metal, for example palladium catalyst and at a temperature of from 30 to 450oC, 1,1,1,3,3-pentafluoropropane can be produced with high selectivity, which constitutes 80% or more.

In accordance with the third invention offers a highly efficient industrial method to produce 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane with high yield and at low cost, in which propargylamine having the General formula (1), is subjected to a fluorination reaction using hydrogen fluoride in the presence of trihalogen antimony and/or pentavalent antimony in the liquid phase, and the amount of fluoride in the system 5 times or more larger than the number trihalomethyl invention, 1,1,2,3,3-hexachloropropene can be highly economical and easy to carry out industrially, in which 1,1,1,2,2,3,3-Heptafluoropropane subjected to reaction with an aqueous solution of alkali metal hydroxide in the presence of a phase transfer catalyst.

The following examples of carrying out the invention are given only for purposes of illustration, however, they can be modified based on the technical concept of the invention.

Example 1. 20 cm3palladium catalyst on charcoal in 0.5% concentration were loaded into made of SUS316 reaction vessel having an inner diameter of 2 cm and a length of 40 cm, and then was heated to 250oC in an electric furnace in a stream of nitrogen. After reaching a specified temperature, nitrogen gas was replaced with hydrogen gas, which was temporarily introduced into the vessel. After this pre-gasified 1,1,1,3,3-pendaftar-2,3-dichloropropan and hydrogen gas was introduced into the reaction vessel with 16.7 and 140 cm3/min, respectively. The reaction temperature was maintained at 250oC. After washing with water and drying with calcium chloride produced gases were analyzed by gas chromatography. The results are presented in table. Skorosti flow of gaseous hydrogen and 1,1,1,3,3-pendaftar-2,3-dichloropropane was 140 and 17 cm3/min, respectively. The reaction temperature was 270oC. the Results are presented in table. 1.

In accordance with the specified data target compound can be obtained by the reaction carried out according to the first invention, at 100% conversion and a high degree of selectivity component is not less than 80%.

Example 3. 20 cm3palladium and zirconium catalyst on charcoal at 0.5% and 0.25% concentrations, respectively, were loaded into made of SUS316 reaction vessel having an inner diameter of 2 cm and a length of 40 cm, and then was heated to a temperature of 250oC in an electric furnace in a stream of nitrogen. After reaching a specified temperature, nitrogen gas was replaced with hydrogen gas, which was temporarily introduced into the reaction vessel. After this pre-gasified 1,1,1,3,3-pendaftar-2,3-dichloropropan and hydrogen gas was introduced into the reaction vessel with 16.7 and 140 cm3/min, respectively. The reaction temperature was maintained at 250oC. After washing with water and drying with calcium chloride produced gases were analyzed by gas chromatography. The data obtained are presented in table. 2.

3/min, respectively. The data obtained are presented in table. 2.

Example 5. 20 cm3palladium and vanadium catalyst on charcoal at 0.5% and 0.25% concentrations, respectively, were loaded into made of SUS316 reaction vessel having an inner diameter of 2 cm and a length of 40 cm, and then was heated to a temperature of 250oC in an electric furnace in a stream of nitrogen. After reaching a specified temperature, nitrogen gas was replaced with hydrogen gas, which was temporarily introduced into the reaction vessel. After this pre-gasified 1,1,1,3,3-pendaftar-2,3-dichloropropan and hydrogen gas was introduced into the reaction vessel with 16.7 and 140 cm3/min, respectively. The reaction temperature was maintained at 250oC. After washing with water and drying with calcium chloride produced gases were analyzed by gas chromatography. The data obtained are presented in table. 2.

Example 6. The reaction was carried out in the same conditions as in example 5, except that the flow rate of the hydrogen gas and 1,1,1,3,3-pendaftar-2,3-dichloropropane was 280 and 32 cm3/min, respectively. The data obtained are presented in table. 2.

In slotsno the second invention, at 100% conversion and a high degree of selectivity component is not less than 80%.

Example 7. In a 500-ml autoclave made of Hastelloy (alloy) and is equipped with a fridge, downloaded and 29.9 g (0.1 mol) SbCl5and then, after cooling, was added 300 g (15 mol) of hydrogen fluoride (HF). After that, the temperature was slowly raised and the reaction was carried out for 3 hours at a temperature of 80oC. Then was added 1,1,1,2,3,3-hexachloropropene and hydrogen fluoride at 0.2 and 1.2 mol/h, respectively, while maintaining the temperature of 80oC. the Reaction pressure was controlled in the range of 9 to 11 kg/cm2so that the mass of the reactor remained constant.

During the reaction hydrogen chloride and the resulting product was removed from the top of the refrigerator and the washing was carried out with water the product was captured using traps cooled with dry ice. After adding 249 g (1 mol) 1,1,1,2,3,3-hexachloropropene reaction was stopped.

After termination of the reaction the pressure was slowly lowered and the contents were collected. The result is 190 g of organic matter.

Using GLC (gas liquid chromatography), it was found that 97% of the received product sostav the p-2,3,3-trichlorpropane, which is the intermediate reaction product, and halogenated propane, to which was added chlorine was not detected.

Example 8. In a 500-ml autoclave made of Hastelloy (alloy) and is equipped with a fridge, downloaded and 29.9 g (0.1 mol) SbCl5and then, after cooling, was added 300 g (15 mol) of hydrogen fluoride. After that, the temperature was slowly raised and the reaction was carried out for 3 h at 80oC. Then was added 1,1,1,2-titrator-3,3-dichloropropane and hydrogen fluoride at 0.2 and 0.6 mol/h, respectively, while maintaining the temperature of 80oC. the Reaction pressure was controlled in the range of 9 to 11 kg/cm2.

During the reaction hydrogen chloride and the resulting product was removed from the top of the refrigerator and the washing chloride water the obtained product was collected using traps cooled with dry ice. After adding 183 g (1 mol) 1,1,1,2-titrator-3,3-dichloropropene reaction was stopped.

After termination of the reaction the pressure was slowly lowered and the contents were collected. As a result received 177 g of organic matter.

Using gas-liquid chromatography, it was found that 98.5% of the obtained product was the target 1,1,1,2,3,3 which is the intermediate reaction product, and halogenated propane, to which was added chlorine was not detected.

Example 9. In a 500-ml autoclave made of Hastelloy (alloy) and is equipped with a fridge, downloaded and 29.9 g (0.1 mol) SbCl5and then, after cooling, was added 300 g (15 mol) HF. The temperature was slowly raised and the reaction was carried out at 80oC for 3 hours then was added 1,1,1-Cryptor-2,3,3-trichlorpropane and HF at 0.2 and 0.8 mol/h, respectively, while maintaining the temperature of 80oC. the Reaction pressure was controlled in the range from 10 to 12 kg/cm2.

During the reaction hydrogen chloride and the resulting product was removed from the top of the fridge, and then hydrogen chloride was washed with water and the obtained product was captured using traps cooled with dry ice. After adding 199 g (1 mol) of 1,1,1-Cryptor-2,3,3-trichlorpropane reaction was stopped.

After termination of the reaction the pressure was slowly lowered and the contents were selected, resulting in a received 198 g of organic matter.

Using gas-liquid chromatography, it was found that 98% of the obtained product was the target 1,1,1,3,3-pendaftar-2,3-dichloropropan (yield 96%).

The main side probirovanie propane, to which was added chlorine was not detected.

Example 10. The reaction was carried out under the same conditions as in example 7, except that a 500-ml autoclave made of Hastelloy (alloy) and is equipped with a fridge, downloaded and 29.9 g (0.1 mol) SbCl517.9 g (0.1 mol) SbF3.

Thus, there was obtained the product, namely, 196 g of organic matter. With GC, it was found that 98% of the obtained product was the target 1,1,1,3,3-pendaftar-2,3-dichloropropan (yield 94%). The main by-product was 1,1,1-titrator-2,3,3-trichlorpropane, and the connection to which was added chlorine was not detected.

According to the results obtained with the reaction carried out in accordance with the third variant of the invention, 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane can be easily obtained with high yield.

Example 11. In a 500-ml round-bottom flask equipped with fridge Dimroth and addition funnel, was loaded 285,5 g (1 mol) 1,1,1,2,2,3,3-Heptafluoropropane and 0.3 g (0.1 mmol) of the chloride tetrabutylammonium. Then with vigorous stirring and at a temperature of 40oC for one hour drop was added 250 ml of an aqueous solution of KOH in 20% concentration. After the head of the Rial, namely, 1,1,1,2,2,3,3-Heptafluoropropane disappeared, and the organic layer consisted only of 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred into a separating funnel to separate an organic layer. After washing with saturated brine (twice) layer was dried with magnesium sulfate and received 237 g (95%) of the crude 1,1,1,2,3,3-hexachloropropene.

Example 12. In a 500-ml round-bottom flask equipped with fridge Dimroth and addition funnel, was introduced 285,5 g (1 mol) 1,1,1,2,2,3,3-Heptafluoropropane and 0.3 g (0.1 mmol) of the chloride of tricaprylate. Then with vigorous stirring and at a temperature of 40oC for one hour drop was added 250 ml of an aqueous solution of KOH in 20% concentration. After complete addition, the reaction was carried out for 1 h Then the stirring was stopped and the lower organic layer was analyzed. The source material, namely 1,1,1,2,2,3,3-Heptafluoropropane disappeared, and the organic layer consisted only of 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred into a separating funnel to separate an organic layer. This layer twice washed with saturated saline, then was dried with magnesium sulfate and received 232 g (93%) of the crude 1,1,1,2,3,3-hexachl the Noah funnel, download 285,5 g (1 mol) 1,1,1,2,2,3,3-Heptafluoropropane and 0.3 g (0.1 mmol) of the chloride tetrabutylphosphonium. After that, when the temperature of the 40oC for one hour drop was added 250 ml of an aqueous solution of KOH in 20% concentration, vigorously stirring the while. After complete addition, stirring was stopped and the lower organic layer was analyzed. The source material, namely 1,1,1,2,2,3,3-Heptafluoropropane disappeared, and the organic layer consisted only of 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred into a separating funnel to separate an organic layer. This layer was twice washed with a saturated saline solution, dried by magnesium sulfate and received 239 g (96%) of the crude 1,1,1,2,3,3-hexachloropropene.

Example 14. In a 500-ml round-bottom flask equipped with fridge Dimroth and addition funnel, was introduced 285,5 g (1 mol) 1,1,1,2,2,3,3-Heptafluoropropane and 0.3 g (0.1 mmol) of the chloride of trioctylamine. Then at a temperature of 40oC for one hour drop was added 250 ml of an aqueous solution of KOH in 20% concentration, vigorously stirring the while. After complete addition, the reaction was carried out for 2 hours and Then the stirring was stopped and the lower organic layer was analyzed. The source s.

The reaction solution was transferred into a separating funnel to separate an organic layer. This layer was twice washed with a saturated saline solution, dried by magnesium sulfate and received 237 g (95%) of the crude 1,1,1,2,3,3-hexachloropropene.

Comparative example 1. In a 500-ml round-bottom flask equipped with fridge Dimroth and addition funnel, was introduced 285,5 g (1 mol) 1,1,1,2,2,3,3-Heptafluoropropane. After that, when the temperature of the 40oC and vigorous stirring for one hour drop was added 250 ml of an aqueous solution of KOH in 20% concentration. After complete addition, the reaction was carried out for 3 hours and Then the stirring was stopped and the lower organic layer was analyzed.

After a short reaction the organic layer 63% was from the source material, namely 1,1,1,2,2,3,3-Heptafluoropropane, and the conversion rate was 37%.

According to the obtained presolution 1,1,1,2,3,3,3-hexachloropropene can be easily obtained by using the reaction carried out in accordance with the fourth invention.

Example 15. With reactions carried out in the same conditions as in example 11, except that instead of the aqueous 20% solution of KOH was used the Reaction was carried out in the same conditions, as in example 7, except that a 500-ml autoclave made of Hastelloy (alloy) and is equipped with a fridge, downloaded and 29.9 g (0.1 mol) SbCl5and 22.9 g (0.1 mol) SbCl3.

Thus, the received product, namely 194 g of organic matter. Using gas-liquid chromatography, it was found that 98% of the obtained product was the target 1,1,1,3,3-pendaftar-2,3-dichloropropan (yield 93%). The main by-product was 1,1,1-titrator-2,3,3-trichlorpropane, and the connection to which was added chlorine was not detected.

1. The method of obtaining 1,1,1,3,3-pentafluoropropane using reduction with hydrogen in the gas phase in the presence of a catalyst is a noble metal on a carrier, characterized in that the restoration is subjected 1,1,1,3,3,-pendaftar-2,3-dichloropropan.

2. The method according to p. 1, characterized in that as the carrier for catalyst using a carrier selected from the group of activated carbon, silica gel, titanium oxide or zirconium dioxide.

3. The method according to PP.1 and 2, characterized in that the used catalyst with a concentration of the noble metal on the carrier is from 0.05 to 10%.

4. The method according to PP.1 to 3, characterized in that cachedout with at least a stoichiometric amount of hydrogen.

6. The method according to PP.1 to 5, characterized in that the process is conducted at a temperature of from 30 to 450oC.

7. The method of obtaining 1,1,1,3,3-pentafluoropropane using reduction with hydrogen in the gas phase in the presence of a catalyst is a noble metal on a carrier, characterized in that the restoration is subjected 1,1,1,3,3, -pendaftar-2,3-dichloropropan and use the catalyst additionally containing zirconium or vanadium.

8. The method according to p. 7, characterized in that as the carrier for catalyst using a carrier selected from the group of activated carbon, silica gel, titanium oxide or zirconium dioxide.

9. The method according to p. 8, characterized in that the use of catalyst, concentration of metal selected from zirconium, vanadium and palladium, on the media, from 0.05 to 10 wt.%.

10. The method according to PP.7 to 9, characterized in that the process is conducted in at least the stoichiometric amount of hydrogen.

11. The method according to PP.7 to 10, characterized in that the process is conducted at a temperature of from 30oC to 450oC.

12. The method of obtaining 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane by reacting halogenated propene with hydrogen fluoride in the liquid phase in the presence of katarismo I

where X and Y denotes Cl or F, as the catalyst take three - and/or Penta-antimony halide, the molar quantity of hydrogen fluoride in 5 or more times the amount of tri - and/or pentavalent antimony.

13. The method according to p. 12, characterized in that the starting halogenated propene and hydrogen fluoride is introduced into the reaction system from which obtained at that 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane taken at a constant reaction pressure.

14. The method according to PP.12 or 13, characterized in that as a halogenated propene General formula I use 1,1,1,2,3,3-hexachloropropene, and 1,1,1,3,3-pendaftar-2-halogeno-3-chloropropane represents 1,1,1,3,3-pendaftar-2,3-dichloropropan.

15. The method of obtaining 1,1,1,2,3,3-hexachloropropene the dehydrochlorination 1,1,1,2,2,3,3-Heptafluoropropane using a hydroxide of an alkali metal, wherein the alkali metal hydroxide used in the form of an aqueous solution and the process is conducted in the presence of a catalyst phase transfer.

16. The method according to p. 15, characterized in that the catalyst phase transfer use tetraalkylammonium salt.

17. The method according to p. 15, characterized in that the catalyst Ana, characterized in that 1,1,1,2,3,3-hexachloropropene obtained by the method according to any of paragraphs 15 to 17, is used to produce 1,1,1,3,3-pendaftar-2,3-dichloropropane in accordance with the method according to any of paragraphs.12 to 14, and the specified 1,1,1,3,3-pendaftar-2,3-dichloropropan used to produce 1,1,1,3,3-pentafluoropropane in accordance with the method according to any of paragraphs.1 - 10.

19. The method of obtaining 1,1,1,3,3-pendaftar-2,3-dichloropropane, characterized in that 1,1,1,2,3,3-hexachloropropene obtained by the method according to any of paragraphs.15 - 17, used to produce 1,1,1,3,3-pendaftar-2,3-dichloropropane in accordance with the method according to any of paragraphs.12 - 14.

20. The method of obtaining 1,1,1,3,3-pentafluoropropane, wherein 1,1,1,3,3-pendaftar-2,3-dichloropropan obtained by the method according to any of paragraphs.12 to 14, is used to produce 1,1,1,3,3-pentafluoropropane in accordance with the method according to any of paragraphs.1 - 10.

Priority points:

29.12.92 on PP.1 - 6;

10.06.93 on PP.7 - 11;

29.12.92 on PP.12 - 13;

10.06.93 on PP.14 - 17.

 

Same patents:
The invention relates to an improved method of producing 1,1,1-Cryptor-2-chlorethane (denoted further as HCFC a), carried out by hydropericardium trichloroethylene (TAE) in the gas phase in the presence of chromium oxide and/or acceptedof chromium or chromium fluoride as catalyst

The invention relates to chemical technology of obtaining PFC, in particular, to a method for producing 2-Gidropribor-2-methylpropane (PPMP), which is an intermediate in various organic syntheses

The invention relates to a method for 1,1,2,2,3-pentafluoropropane

The invention relates to a new partially fluorinated alkanal having a tertiary structure and containing from 4 to 9 carbon atoms

The invention relates to a chemical process, in particular to a method for producing bis-formativos ester by the interaction of formaldehyde and hydrogen fluoride, and to a method for deformity, comprising a step for bis-formativos ether of formaldehyde and hydrogen fluoride

The invention relates to the chemical industry and is intended to receive performancenow, namely freon (Halocarbon 116) and OCTAFLUOROPROPANE (Halocarbon 218), used as a means of dry etching in microelectronics

The invention relates to the chemical industry and can be used to obtain 1,1,2,2-Tetrafluoroethane (HFC 134), which is a promising, low-impact-halon

The invention relates to the chemical industry and can be used to remove impurities of vinyl chloride 1,1-differetn (HFC 152a) - ozone-safe refrigerant) used as a refrigerant, porofor, raw materials for the synthesis of organofluorine products

The invention relates to the field of chemistry of aromatic organochlorine compounds, and in particular to a method for producing 1,1-dichloro-2,2-(4-chlorophenyl)ethylene

The invention relates to organic synthesis, in particular, to a catalytic process for the production of vinylidenechloride, which is the raw material for plastics, composite materials, paints, adhesives and other valuable products

The invention relates to organic synthesis, in particular, to methods for CIS - and TRANS-1,2-dichlorethylene that are used in the process of synthesis of polymeric materials, adhesives and resins
The invention relates to organic and Organoelement chemistry, namely, the processes of detachment of atoms of halogen from various halogenated compounds

The invention relates to a method of dehydrocorydaline 1,1-bis(R-phenyl)-2,2,2-trichloroethanol

The invention relates to a process dihydrochloride (pyrolysis) of organochlorine compounds in the presence of heterogeneous catalysts for cleaning emissions, disposal of toxic compounds and produce useful products, in particular the processing of 1,2-dichloroethane with the aim of obtaining vinyl chloride

The invention relates to the production of fluorine-containing monomers, namely the synthesis of vinyl fluoride, 1,1-defloration and triptorelin used as feedstock to produce different grades of fluoropolymers

The invention relates to chemical technology perhalogenated, namely the method of production of mono - and dibromopropanol or their chlorinated analogues, which are used as intermediates in the synthesis of dyes, pharmaceuticals, monomers, etc
Up!