Method of reduction of (-halogenketones to secondary (-halogenspirits

FIELD: chemistry.

SUBSTANCE: method involves a stage of interaction of one or more α-halogenketones with general formula I , where each of "X" independently represents a halogen atom, except fluorine, a hydrogen atom and "Z" represents a halogen atom, except fluorine; with molecular hydrogen in the presence of heterogeneous catalyst, containing a transition metal, where the catalyst is a metallic salt, which is saturated with the catalyst carrier, where the metal consist of iridium, ruthenium or their mixture. The metal catalyses hydrogenation of all carbonyl groups of α-halogenketons to alcohol groups, at temperature from 1° to 200°C and pressure of at least 14 abs. pound/square inch with formation of one or more α-halogenspirits with general formula II . The invention also relates to the method of obtaining epoxides (alternatives), to the method of obtaining epi-halogenhydrine (alternatives) and to the method of obtaining propylene oxide (alternatives).

EFFECT: improved activity of the catalyst.

3 tbl, 3 ex

The present invention relates to a method for α-galogenidov from α-halogenated. In particular, the present invention relates to a method of synthesis of α-galogenidov by hydrogenation α-halogenated, α-halogenerte obtained by the method according to the present invention, used to obtain epoxides.

There are many ketones, known from the prior art, and hydrogenation of ketones is not something unusual. However, α-halogenation due to the unstable relations halogen-carbon bonds are more reactive than other ketones, and professionals in this field know that it is very difficult to carry out selective hydrogenation α-halogenated to α-galogenidov. So still there is a need for an economical and efficient method of hydrogenation α-halogenated.

α-halogenation known from the prior art, can be turned into α-halogenerte a variety of known ways. For example, in some literature references describe recovery α-halogenated using homogeneous catalytic systems. For example, U.S. patent No. 4024193 describes how homogeneous hydrogenation using active forms of ratemycameltoe, represented by the following formula RuHCl(PR₃ )₃to restore the activated carbonyl compounds, including α-chloretone, such as 1,3-dichloroacetone and α-chloracetophenone. The yields and selectivity of the reactions in U.S. patent No. 4024193 not specified.

The Japan patent No. 63-297333 describes how to obtain 1,3-dichloro-2-propanol from 1,3-dichloroacetone using aluminiumprofile as a homogeneous catalyst with an excess of isopropanol as a reagent transport of hydrogen. Selectivity of 95 percent or less can be obtained when using the method according to the Japan patent No. 63-297333, but may not be used in a number of aluminiumprofile less than 0.01 equivalent.

The Japan patent No. 09-104648 describes a method of hydrogenation α-halogenated, including α-chloretone, such as 1,3-dichloroacetone, with the formation of 1,3-dichloro-2-propanol using homogeneous ruthenium complex containing cyclopentadienyl ligand. When using the method according to the Japan patent No. 09-104648 achieved selectivity from 91 percent to 98 percent in respect of 1,3-dichloro-2-propanol and less than 10,000 complaints installed at successive periodic addition α-halogenation.

WO 9800375 A1 and EP 295890 A2 describe how asymmetric hydrogenation α-halogenated, such as chloroacetone, obtaining chiral alcohols with use the of homogeneous complexes of ruthenium, iridium, rhodium, rhenium, cobalt, Nickel, platinum, palladium containing chiral ligands.

It is also well known that α-halogenerte used for the synthesis of epoxides. For example, the above-mentioned Japan patent No. 09-104648 and the Japan patent No. 63-297333 describe a method of producing epichlorohydrin method comprising the following three stages:

(1) α-chlorination of acetone molecular chlorine in the presence of IDataReader promoter and literorica, leading to the formation of 1,3-dichloroacetone;

(2) hydrogenation of 1,3-dichloroacetone in the presence of a homogeneous catalyst, leading to the formation of 1,3-dichloro-2-propanol; and

(3) the cyclization of 1,3-dichloropropanol base, leading to the formation of epichlorohydrin.

The limitation of all the above methods is the need for a homogeneous catalyst to perform selective recovery α-halogenated. The use of a homogeneous catalyst in the above methods limits the modes of operation of the reactor, and the catalyst separation and reuse are difficult task. In addition, it is desirable to provide a heterogeneous catalyst that allows you to recover α-halogenation with selectively comparable to restore α-halogenation in the presence of homogeneous catalysts, but with the additional is diversified benefits for the media, in a heterogeneous form. Preferably, the heterogeneous catalyst was allowed to carry out recovery method using a catalyst without the need for separation of the catalyst.

Therefore, the present invention is to develop technically feasible and easily controlled method of effective recovery α-halogenation, leading to the formation of α-galagedera, when using a heterogeneous catalyst.

Another objective of the present invention is to develop an improved method of hydrogenation to obtain α-galogenidov from α-halogenating when using a heterogeneous catalyst.

Also the purpose of this method is to provide such a method in which used pressure and temperature allows easy operation more cost-effective manner.

Also to the objectives of the present invention is the development of the prior art; and other objectives will become apparent in the future.

One aspect of the present invention is a method of obtaining α-galagedera, including the stage of interaction α-halogenation with a hydrogenating agent such as elemental hydrogen in the presence of a heterogeneous catalyst containing a transition metal, under such conditions, in which is formed α-Halogens the RTI.

The method according to the present invention may be represented by the following General equation:

The second aspect of the present invention is a method of producing epoxides, which includes stages:

(1) hydrogenation α-halogenation education α-galagedera, as described in the first aspect of the present invention; and

(2) the cyclization of α-galogenidov to obtain epoxides.

The method according to the present invention is based on the use of heterogeneous catalyst, thereby simplifying the operation mode of the reactor and facilitates separation/reuse of the catalyst.

One of the key aspects of the present invention is to detect the heterogeneous catalyst, which allows you to perform such selective hydrogenation. The method according to the present invention is also suitable for the synthesis of epoxides from α-galogenidov.

Currently α-halogenic can be effectively and successfully obtained industrially convenient way to and from readily available materials.

The catalyst used in the method according to the present invention, is a solid and therefore can be easily isolated from the reaction mixture and is easily separated from the product.

The method according to the present invention allows to obtain α-halogenerte from α-halogene is new. α-halogenation of the present invention represented by the following formula I.

The formula I

where each "X" independently denotes a halogen atom except fluorine atom, a hydrogen atom or organic group, and Z means a halogen atom except fluorine atom. 1,3-dichloroacetone is one example of α-halogenation formula I.

α-halogenerte of the present invention represented by the following formula II.

Formula II

where each "X" independently denotes a halogen atom except fluorine atom, a hydrogen atom or organic group, and Z means a halogen atom except fluorine atom. 1,3-dichloro-2-propanol is one example of α-galagedera formula II.

Examples of suitable α-halogenated suitable for the present invention include: 1-chloroacetone, 1,3-dichloroacetone; 1,3-dibromoacetone; 1,1,3-trichloroethan and mixtures thereof. α-halogenation used in the present invention, it is most preferable mean 1,3-dehalogenation to obtain 1,3-dihalogen-2-propanol and 1-halogenation to obtain 1-halogen-2-propanol. 1,3-dehalogenation represented by the following formula.

Formula III

where each "X" independently denotes a halogen except the receiving fluoride. "X" in the above formula III preferably denotes iodine, chlorine or bromine, and most preferably chlorine.

Hydrogenation α-halogenation carried out by interaction with a hydrogenating agent. Hydrogenating agent, useful in the present invention may be, for example, molecular hydrogen, alcohol or a combination of them. Hydrogenating agent means preferably molecular hydrogen. Examples of suitable alcohols useful in the present invention, can serve as a primary or secondary alcohols, such as methanol, ethanol, and C₃-C₁₀primary or secondary alcohols. Preferably the alcohol means methanol. Examples of other secondary alcohols useful in the present invention, is described in U.S. patent No. 2860146.

During the interaction according to the present invention consumes one mole of the hydrogenating agent per mole get α-galagedera. Usually at least 0.6 mol of hydrogenating agent per mole α-halogenation consumed in the course of interaction, preferably at least 0.75 moles hydrogenating agent per mole α-halogenation consumed in the course of interaction, more preferably at least 0.9 moles and most preferably at least 1 mol consumed in the course of interaction. When less than 1 mole hydrogenating agent per mole α-halogenation is consumed in the course of interaction, complete conversion α-galagedera cannot be attained. However, not all hydrogenating agent must be put at the beginning of the interaction. Hydrogenating agent can be added incrementally or continuously as the reaction. In this case the reaction mixture at some particular time period may contain a stoichiometric excess of α-halogenation in relation to the hydrogenating agent. As one of the embodiments of the present invention an excess of the desired hydrogenating agent can be used to complete the conversion α-halogenation in α-halogenic during interaction. Typically, for example, can be used an excess of hydrogenating agent from 10 to 20 percent.

The maximum number of source hydrogenating agent does not play a decisive role and is determined by practical considerations, such as the pressure, the efficiency of the reactor and security. When the source of the hydrogenating agent is gaseous, the amount of hydrogenating agent preferably should be at least sufficient to provide the desired pressure. However, in most cases, the reactor preferably contains not more than 1,000 moles of molecular hydrogen per mole α-halogenation and more preferably contains not more than 100 moles of molecular hydrogen on m is l α -halogenation. Gaseous sources hydrogenating agent, such as molecular hydrogen, is preferably used according to the known methods for mixing gaseous reagent with the liquid reaction mixture, such as bubbling gas through the mixture with stirring or dissolution of hydrogen under pressure.

The interaction of the present invention occurs in the presence of a heterogeneous catalyst containing a transition metal. The transition metal used in the heterogeneous catalyst of the present invention, can serve one or more metals selected from groups IB, IIB or IIIA-VIIIA of the periodic table of elements, as currently adopted according to the International Union of pure and applied chemistry (IUPAC). The metal catalyst suitable for the present invention are chosen so that the conditions of interaction between the metal catalyzed hydrogenation of all carbonyl groups of the molecule α-halogenation to alcohol groups, essentially without affecting the halogen-related molecule α-halogenation. The metal catalyst is preferably selected from group VIIIA of the accepted IUPAC periodic table, including, for example, iron, cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and mixtures thereof. More preferably, the metal catalyst selected from the group including ruthenium, iridium, rhodium, palladium, platinum and mixtures thereof. Most preferably, the metal catalyst is chosen from the group comprising ruthenium, iridium or mixtures thereof.

An illustrative example of the catalyst of the present invention can be, for example, mixed metal catalysts iridium/ruthenium described in published European patent application 1140751. The atomic ratio of iridium metal and metal ruthenium in the catalyst is usually from 0.02 to 15, preferably from 0.05 to 10, more preferably from 0.15 to 8 and most preferably from 0.3 to 2.0.

Heterogeneous catalyst, useful in the present invention, can be, for example, the transition metal deposited on the insoluble carrier or adsorbed to an insoluble carrier, such as silicon dioxide, sililirovany silicon dioxide, carbon, aluminum oxide, titanium oxide, zirconium dioxide, magnesium oxide and other conventional media known from the prior art, as described in Poncelet et al. editors,Preparation of Catalysts III, New York, 1983; P.N. Rylander,Hydrogenation Methods, Academic Press, London, 1985; P.N. Rylander,Catalytic Hydrogenation Over Platinum Metals, Academic Press, New York, 1967; P. Rylander,Catalytic Hydrogenation in Organic Syntheses, Academic Press, New York, 1979. Heterogeneous catalyst according to the present invention can be also the transition metal coordination-related ligands, chemical the key connected with polymer resin, for example ruthenium on pospisilova polystyrene. The catalyst is usually represented in the form of granules or tablets. The number of active catalyst on the carrier is usually from 0.1 percent (percent) to 25 percent and preferably from 0.5 to 15 percent.

One of the advantages of the use of heterogeneous catalyst in the method according to the present invention is to isolate the catalyst from the reaction solution by various methods, such as filtering.

The ideal ratio of catalyst and reagents used in this method varies depending on the flow velocity, the layer size, temperature, desired degree of conversion, chemicals and other factors that determine this way. Typically, the layer of the heterogeneous catalyst contains from 0.0001 to 100 moles of the metal catalyst per mol passing through the layer α-halogenation per hour.

The interaction of the present invention optionally, but preferably is carried out in the presence of a solvent. Used solvent is preferably inert to all reagents under conditions of interaction. The solvent can be chosen so that: (1) the solvent does not boil in the interface, and (2) α-halogenic can be isolated from the solvent, e.g. by distillation, extractively any other known means of selection.

Examples of suitable solvents suitable for the present invention include aromatic and aliphatic hydrocarbons, chlorinated hydrocarbons, ethers, slimy, simple glycol ethers, esters, alcohols, amides, and mixtures thereof. Specific examples of solvents useful in the present invention include toluene, cyclohexane, hexane, methylene chloride, dioxane, dimethyl ether, diglyme, 1,2-dimethoxyethane, ethyl acetate, methanol, NMP, and mixtures thereof. The amount of solvent used in the present invention, is not critical and is determined primarily by practical considerations, such as efficiency of the reactor. Usually the amount of solvent present in the reaction mixture varies from 0 to 99.99 mass%.

In the most preferred cases, the reaction mixture according to the present invention mainly contains at least 5 mass% α-halogenation, preferably 10 mass% and most preferably at least 20 mass%. The reaction mixture may be pure (i.e., the reaction mixture may contain essentially 100 weight percent α-halogenation), but if you use a solvent in addition to α-halogenation, the reaction mixture preferably contains not more than 90 mass is% α -halogenation and more preferably not more than 80 mass% α-halogenation.

When the reaction mixture contains alcohol, the interaction is preferably carried out under conditions essentially the absence of a strong mineral acids such as hydrochloric acid, which can lead to reduced selectivity and outputs. "In essence, the absence of strong mineral acids means that the concentration of such acids is below a sufficient level, so that the acid does not catalyze the formation of significant outputs ketals of α-halogenation and alcohol. For example, levels of ketals formed by acid catalyzed interaction between α-halogenatom and alcohol in the reaction mixture can be generally less than 50 mass percent, preferably less than 20 mass percent, and most preferably below 1 percent.

Without going into theoretical justification, it is believed that a strong acid catalyzes the interaction of α-halogenation with alcohol, leading to the formation of unwanted Catala. In cases where the reaction mixture contains a minor amount of hydrochloric acid, it is preferable to carry out interaction in the presence of an acid acceptor, if the reaction mixture contains the alcohol, to prevent the formation of ketala.

Examples of acceptor the acids, used in the present invention include carbonates of alkali metals; bicarbonates of alkali metals; carboxylates of alkali metals; ammonium and phosphonocarboxylate, bicarbonates and carbonates; epoxides and mixtures of these compounds. Specific examples of acid acceptors include sodium carbonate, sodium bicarbonate, ammoniumbicarbonate, ethylene oxide, propylene oxide, butylenes, epichlorohydrin and mixtures thereof. The epichlorohydrin is the preferred epoxide, employees acid acceptor.

Temperature interaction is not critical, provided that all the reactants and catalyst are in close contact with each other. However, lower temperatures require longer implementation of the response. The reaction temperature is preferably at least -10°C, more preferably at least 20°C and most preferably at least 50°C. the reaction Temperature is preferably below 250°C, more preferably not exceeding 150°C and most preferably no higher than 120°C. the reaction Temperature is preferably from 0 to 200°C and more preferably from 50 to 120°C.

The pressure of the reaction is not critical as long, yet provides a sufficient amount of hydrogenating agent, such as hydrogen, for which EOI is to interact in the reaction mixture. The pressure is preferably at least 14 pounds per square inch absolute value (abspann psi) (97 kilopascals (kPa), 1 atmosphere), and more preferably at least 50 abston psi (340 kPa, 3.4 atmospheres). The pressure is preferably not higher than 3.000 abston psi (21 MPa, 204 atmospheres). The increased pressure leads to reduction of the time of interaction.

Typically, the time of interaction in hydrogenation reactions of the present invention is less than 72.000 seconds and preferably from 36.000 to 180 seconds is sufficient to achieve conversion, close to theoretical 1 gram α-halogenation to α-galagedera per gram of catalyst.

In the preferred process conditions α-halogenation catalytically interact with an excess of hydrogen at a temperature of from 0 to 200°C during the interaction from 36.000 up to 180 seconds for 1 gram α-halogenation per gram of catalyst, followed by separation of the desired reaction product.

The product of the interaction of this invention is α-halogenic with the structure derived from α-halogenation. The product can be isolated by known methods such as extraction or distillation. The product can be selected with such low yields, as 2 percent, however, for economic purposes, the product usually is on the exhale, at least 60% yields (calculated on the original amount α-halogenation) and preferably produce at least 80 percent outputs, more preferably, at least 90 percent o and most preferably at least 95 percent of the exits.

α-halogenic obtained by the method according to the present invention, is an important intermediate product of the reaction. The way to get α-galagedera of the present invention is particularly useful stage of the common way obtain epoxides. Immediately after receiving α-galagedera using reaction reduction/hydrogenation of the present invention α-halogenic can be cycletour order to obtain epoxide is well known from the prior art methods. For example, α-halogenerte are used to obtain epoxides by treatment α-galagedera base. Therefore, the present invention can be used for a method of synthesis of epoxides, such as epichlorohydrin and propylene oxide, for example, a common method comprising the following stages:

(1) hydrogenation α-halogenation education α-galagedera and

(2) the cyclization of α-galagedera under the action of bases, leading to the formation of epoxide.

Another options is the ant get epoxide front of the stage hydrogenation α -halogenation can be obtained by halogenoalkanes ketone, leading to the formation of α-halogenation.

The key stage of the method according to the present invention is a selective hydrogenation α-halogenation to α-galagedera carried out so that the carbon-chlorine α-halogenation remain unaffected during hydrogenation.

In particular, the method according to the present invention can be used as one stage of the production method, for example, epichlorhydrin or of propylene oxide from acetone. To illustrate the method, for example, a method of obtaining epichlorhydrin can be presented in detail as follows.

At the stage (1) method of producing epichlorhydrin acetone halogenous, receiving 1,3-dehalogenation. This stage is obtaining 1,3-dichloroacetone described, for example, in U.S. patent No. 4251467 and JP 9255615.

At stage (2) of the method according to the present invention 1,3-dehalogenation hydronaut with the formation of 1,3-dihalogen-2-propanol. Preferred embodiments of the a stage (2) described in this application above. For example, one embodiment of the method according to the present invention includes a step between 1,3-dehalogenation, with at least a stoichiometric amount of molecular hydrogen in the presence of ruteniysoderzhaschim, iridectomies is or mixed ruthenium-iridium-metal-containing catalyst and a suitable solvent, such as dioxane, which leads to the formation of 1,3-dihalogen-2-propanol.

At stage (3) this method of 1,3-dihalogen-2-propanol is converted into epichlorhydrin. This stage (3) is well known in the field of reception of epichlorhydrine. Reaction stage (3) is usually carried out by reacting 1,3-dihalogen-2-propanol with a strong base, such as aqueous alkali metal hydroxide, such as sodium hydroxide. Examples of interaction at the stage (3) is described in U.S. patent No. 2860146 and patent Australia No. 630238.

Methods for producing epoxides by using the present invention may contain in addition to the stage (2) one or more of the above stages (1), (2) and (3). Methods for producing epoxides preferably include stage (1) and (2), more preferably include stage (1), (2) and (3).

In the methods for producing epoxides, such as epichlorhydrin or propylene oxide, it is possible to proceed from a mixture containing α-halogenation together with other ketones, isomers or reagents. In such cases, preferably, selected α-halogenation, such as 1,3-dehalogenation to obtain epichlorhydrin or such as 1-halogenation to obtain propylene oxide was the predominant ketone and mainly to the resulting product was epichlorhydrin or propylenic the ID accordingly. Because of the possibility that the resulting product will be a mixture of epichlorhydrin and propylene oxide, it is desirable to regulate the amount used in the way α-halogenated to provide the desired product in sufficient quantity. Under "pre-emptive" here is understood that the desired product is present in amounts of more than 50 mass percent or more in a mixture of two key α-halogenating components and more than 40 mass percent or more in the mixture of the three principal α-halogenating components. For example, when a mixture of the source compounds, such as 70 percent 1,3-dehalogenation and 30% 1-halogenation, the product will contain essentially 1,3-dihalogen-2-propanol.

The following examples are for illustrative purposes only, and may not be considered as limiting the scope of the present description and attached items. Unless otherwise noted, all parts and percentages are mass.

General experimental procedures

Synthesis of catalyst: catalysts receive, impregnating silica with aqueous solutions of metal salts containing IrCl₃·3H₂O and RuCl₃·H₂O. System of mixed metals are joint impregnation of silica with two metal salts or what robidou salt of one metal (and drying), followed by impregnation of a salt of another metal. The catalysts are dried in air and then pre-restore the current H₂/N₂(5% hydrogen) at 473K (200°C). Then the catalyst is stored and processed on the air.

System reactor A: reactor includes a vessel in the form of a pipe 6,35E-3 m H 3,05E-1 m (0.25 inch H 12 inches) Hastelloy alloy, wrapped tape electric heating element and insulating material, the liquid ring pump and two flow regulator, which feeds 3,55E6 PA (500 psi, calibrated (psig) of hydrogen and nitrogen. The initial mixture of gaseous and liquid feedstock enters the reactor from the bottom and exits through the upper part; after which the raw material mixture flows through the pressure regulator suction in the selection system at ambient pressure and then in a caustic scrubber.

The effect of the reactor And: catalyst loaded into the reactor, removing the exhaust manifold reactor with dropped pressure, add 7,5E-7 m³Sigma glass beads (425-600 microns, washed with acid, and then into the tank add 1E-3 kg of catalyst and reactor type 7,5E-7 m³glass beads. Connect the exhaust manifold and the reactor rinsed with nitrogen at ambient pressure for one hour, then the reactor is heated up to 358K (85°C). After which the reactor is filled with hydrogen to a pressure of 3,55E6 PA (50 pounds per square inch, K.) and after 1/2 hour to start the flow of liquid.

System description reactor B and the actionin this case, use a tank reactor Parr Hastelloy C alloy with a capacity of 300 ml reactor make the catalyst loading and the digester tank vacuum and rinsed three times with nitrogen. The mixture of solvent/α-halogenation Tegaserod, barbotine nitrogen, and added to a Parr reactor with a syringe. In the reactor admit/release nitrogen to a pressure of 250/20 pound per square inch, K. (1.8 MPa/241 kPa) hydrogen pressure up to 100/20 lbs per square inch, K. (793 kPa/241 kPa), then leave under hydrogen pressure of 100 pounds per square inch, K. (793 kPa) and heated to 35°C. the Samples are selected syringe after reducing the pressure of the reactor to less than 15 pounds per square inch, K. (207 kPa).

Analysis: samples analyzed by gas chromatography (GC)using a Hewlett Packard HP-6890 gas chromatograph equipped with a 30 m Rtx-5 capillary column with slotted injection. Approximately 120 μl of the reaction mixture is dissolved in 5E-6 m³(5 ml) of o-dichlorobenzene containing a known amount of chlorobenzene as a GC standard (usually the 0.05 mass percent). "Selectivity" is defined as the ratio of α-galagedera to the resulting combined products.

Example 1

Example 1 demonstrates the effect of a catalyst 8 percentage Ir/2% EN/silicon dioxide is the ratio of hydrogenation of 1,3-dichloroacetone.

In A reactor, was charged to the reactor as described above in the General experimental methods, 1.0 g of the catalyst 8 percentage Ir/2.0 percentage EN/silicon dioxide. Get liquid raw material consisting of a mixture of 10.2 weight percent 1,3 - dichloroacetone/dioxane, and bubbled with nitrogen. The feed rate is 2,2E-9 m³(0,132 CC/min), which corresponds to the time of interaction 4,440 seconds, as indicated previously. As specified in the General experimental methods, 85°C and 500 psi, K. (3,55E6 PA) H₂are the standard terms of engagement. During 80,5 hours periodically take samples of the reaction mixture and analyzed. The results of the analysis are presented in the following table I, where "selectivity" is defined as the ratio of 1,3-dichloro-2-propanol to the resulting combined products.

Example 2

Example 2 demonstrates the effect of a catalyst 8 percentage Ir/2% EN/silicon dioxide in the ratio of hydrogenation of 1-chloroacetone.

In A reactor, was charged to the reactor as described above in the General experimental methods, 1.0 g of the catalyst of 8.0 percent Ir/2.0 percentage EN/silicon dioxide. Get liquid raw material consisting of a mixture of 7.1 weight percent 1-chloroacetone/dioxane, and bubbled with nitrogen. The feed speed is 3,0E-9 m³(of 0.182 CC/min), which corresponds to the time of interaction 4,675 seconds. As specified in the General experimental methods, 85°C and 500 psi, K. (3,55E6 PA) H₂are the standard terms of engagement. During 68,25 hours periodically take samples of the reaction mixture and analyzed. The results of the analysis are presented in the following table II, where the "selectivity" is defined as the ratio of the 1-chloro-2-propanol to the resulting combined products.

Example 3

Example 3 gives the comparison of heterogeneous catalyst based on oxide of platinum (Pt) (catalyst Adams'a) with catalyst 8 percentage Ir/2% EN/silicon dioxide. The catalyst Adams'as described previously in U.S. patent No. 3189656 for the hydrogenation of 1,3-dichloro-1,1,3,3-Tetrafluoroethane to 1,3-dichloro-l,1,3 .3m-titrator-2-propanol.

In reactor B load or 0.025 g of catalyst Adams'a or 0.25 g of catalyst 8 percentage Ir/2% EN/silicon dioxide and the digester tank vacuum and rinsed three times with nitrogen. 1,3-dichloroacetone (2.5 g)dissolved in 1,4-dioxane (50 ml), Tegaserod, barbotine nitrogen, and added to a Parr reactor with a syringe. In the reactor admit/release nitrogen to a pressure of 250/20 pound per square inch, K. (1.8 MPa/241 kPa) hydrogen pressure up to 100/20 lbs per square inch, K. (793 kPa/241 kPa), then leave under hydrogen pressure of 100 pounds per square inch, K. (793 kPa) and heated to 35°C. After 8 hours of interaction of the sample taken by syringe and analyzed GC after reducing the pressure of the reactor to less than 15 pounds per square inch, K. (207 kPa). Rez is ltati analysis for this example 3 are shown below in table III. In table III the results demonstrate that the catalyst Adams'and worse in comparison with catalyst 8 percentage Ir/2% EN/silicon dioxide of the present invention, intended for the hydrogenation of fluorine - α-halogenated, such as 1,3-dichloroacetone.

1. The way to get α-galagedera, including stage of the interaction between one or more α-halogenated following General formula I:

where each "X" independently denotes a halogen atom except fluorine, hydrogen atom and Z denotes a halogen atom except fluorine; with molecular hydrogen in the presence of heterogen the second catalyst, containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture thereof, and the metal catalyzes the hydrogenation of substantially all of the carbonyl groups α-halogenated to alcohol groups, at a temperature of from 1 to 200°and a pressure of at least 14 abston/square inch to form one or more α-galagedera following General formula II:

where each "X" independently denotes a halogen atom except fluorine, hydrogen atom and Z denotes a halogen atom except fluorine.

2. The method according to claim 1, where α-halogenation chosen from the group comprising 1,3-dichloroacetone; 1,3-dibromoacetone; 1-bromo-3-chloroacetone; 1-chloroacetone, 1-bromoacetone or mixtures thereof.

3. The method according to claim 1, where α-halogenation means 1,3-dichloroacetone, and generated α-halogenerator is 1,3-dichloro-2-propanol.

4. The method according to claim 1, where α-halogenation means 1-chloroacetone, and generated α-halogenerator is 1-chloro-2-propanol.

5. The method according to claim 4, where the ratio of molecular hydrogen and α-halogenation equal at least to 0.75:1.

6. The method according to claim 4, where the ratio of molecular hydrogen and α-halogenation equal at least to 0.6:1.

7. The method according to claim 1, where katalizatorami iridium and ruthenium in the atomic ratio of iridium to the ruthenium from 0.02 to 15.

8. The method according to claim 7, where the atomic ratio of iridium to ruthenium is from 0.15 to 8.

9. The method of claim 8, where the atomic ratio of iridium to ruthenium is from 0.3 to 2.

10. The method according to claim 1, where the catalyst comprises a promoter is a metal ion of group I or transition metal.

11. The method according to claim 10, where the promoter is an ion selected from the group, mainly consisting of Li, Na, K, Cs, Mo, W, V, Re, Mn and mixtures thereof.

12. The method according to claim 1, where the catalyst further comprises a coordination-bonding ligand.

13. The method according to item 12, where the ligand is chosen from the group, mainly consisting of phosphines, 1,5-cyclooctadiene (COD), arsinami, Stabenow, carbon monoxide, ethers, cyclopentadienyl, sulfoxidov, aromatic amines and mixtures thereof.

14. The method according to item 13, where the ligand means phosphine.

15. The method according to claim 1, where the heterogeneous catalyst supported on a carrier selected from the group, mainly consisting of carbon, silicon dioxide, aluminum oxide, titanium oxide, Zirconia, cross-linked polystyrene, and combinations thereof.

16. The method according to claim 1, where the heterogeneous catalyst is in the form of a layer of a heterogeneous catalyst in the reactor and where the heterogeneous catalyst is present in the reaction mixture at a ratio of from 0.0001 to 100 moles of the metal catalyst per mol passing through the layer α-galagedera per hour.

17. The method according to claim 1, where the reaction to shift the ü further comprises a solvent.

18. The method according to 17, where the solvent is chosen from the group composed primarily of aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated hydrocarbons, ethers, Klimov, simple glycol ethers, esters, alcohols, amides, water and mixtures thereof.

19. The method according to 17, in which there is a solvent and the reaction mixture contains not more than 90 wt.% α-halogenation.

20. The method according to claim 1, where the reaction mixture further comprises an absorber acid.

21. The method according to claim 20, where the absorber acid chosen from the group composed primarily of carbonates of alkali metals, carbonates of alkali metals; carboxylates of alkali metals; ammonium and phosphonocarboxylates, bicarbonates and carbonates, epoxides, and mixtures of these compounds.

22. The method according to claim 20, where the absorber acid is epichlorohydrin.

23. The method according to claim 1, comprising a stage of interaction α-halogenation, with at least a stoichiometric amount of molecular hydrogen in the presence of ruthenium-containing catalyst, iridium-containing catalyst or a mixed iridium-ruthenium - containing catalyst and solvent.

24. The method of producing epoxides, which includes stages:

(a) interaction of one or more α-halogenated following General formula I:

where each "X" independently denotes a halogen atom except fluorine, hydrogen atom and Z denotes a halogen atom except fluorine; with a hydrogenating agent in the presence of a heterogeneous catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture thereof, at a temperature of from 1 to 200°and a pressure of at least 14 abston/square inch to form one or more α-galogenidov following General formula II:

where each "X" independently denotes a halogen atom except fluorine, hydrogen atom and Z denotes a halogen atom except fluorine; and

(b) interaction of one or more α-galogenidov with base to form one or more epoxides.

25. The method of producing epoxides, which includes stages:

(a) α-halogenation of one or more ketones to form one or more α-halogenated;

(b) recovery of one or more α-halogenated in the presence of a heterogeneous catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture of the OBR is using one or more α -galogenidov; and

(c) interaction of one or more α-galogenidov with base to form one or more epoxides.

26. The method of producing epichlorhydrin, which includes stages:

(a) recovery of 1,3-dehalogenation in the presence of a heterogeneous catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture leading to the formation of 1,3-dihalogen-2-propanol; and

(b) interaction of 1,3-dihalogen-2-propanol with the base with the formation of epichlorhydrine.

27. The method of producing epichlorhydrin, which includes stages:

(a) α-halogenation of acetone with the formation of 1,3-dehalogenation;

(b) recovery of 1,3-dehalogenation in the presence of a heterogeneous catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture leading to the formation of 1,3-dihalogen-2-propanol; and

(c) interaction of 1,3-dihalogen-2-propanol with base, leading to the formation of epichlorhydrine.

28. The method of producing epichlorhydrin, which includes stages:

(a) recovery of 1,3-dehalogenation in mixture with on the natives ketones, where the mixture contains predominantly 1,3-dehalogenation, in the presence of a catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture thereof, to obtain predominantly 1,3-dihalogen-2-propanol; and

(C) the interaction of 1,3-dihalogen-2-propanol with the base with the formation of the product, which is mainly epichlorhydrin.

29. The method of producing propylene oxide, comprising the stage of:

(a) recovery 1-halogenation in the presence of a heterogeneous catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture with the formation of 1,3-dihalogen-2-propanol; and

(b) interaction of 1-halogen-2-propanol with base, leading to the formation of propylene oxide.

30. The method of producing propylene oxide, comprising the stage of:

(a) α-halogenation of acetone with the formation of 1-halogenation;

(b) recovery 1-halogenation in the presence of a heterogeneous catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or their cm is camping with the formation of 1-halogen-2-propanol; and

(C) interaction of 1-halogen-2-propanol with base, leading to the formation of propylene oxide.

31. The method of producing propylene oxide, comprising the stage of:

(a) recovery 1-halogenation in a mixture with other ketones, where the mixture contains mainly 1-halogenation in the presence of a catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture with the formation of 1-halogen-2-propanol; and

(b) interaction of 1-halogen-2-propanol with the base with the formation of the product, which is predominantly propylene oxide.

32. The method of producing epichlorhydrin, which includes stages:

(a) α-halogenation of acetone with the formation of 1,3-dehalogenation,

(b) recovering 1,3-dehalogenation in a mixture with other ketones, where the mixture contains predominantly 1,3-dehalogenation, in the presence of a catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or their mixture, with the formation of predominantly 1,3-dihalogen-2-propanol; and

(c) the interaction of 1,3-dihalogen-2-propanol with the base with the formation of the product, which the advantage is but is epichlorhydrin.

33. The method of producing propylene oxide, comprising the stage of:

(a) α-halogenation of acetone with the formation of 1-halogenation;

(b) recovering 1-halogenation in a mixture with other ketones, where the mixture contains mainly 1-halogenation, in the presence of a catalyst containing a transition metal, where the catalyst is a salt of a metal which is impregnated catalyst carrier, where the metal comprises iridium, ruthenium or a mixture with the formation of predominantly 1-halogen-2-propanol, and

(C) the interaction of 1-halogen-2-propanol with the base with the formation of the product, which is mainly propylene oxide.