Patent Description:
Hydrofluorocarbons (HFC's), in particular hydrofluoroalkenes such tetrafluoropropenes (including <NUM>,<NUM>,<NUM>,<NUM>-tetrafluoro-<NUM>-propene (HFO-1234yf) and <NUM>,<NUM>,<NUM>,<NUM>-tetrafluoro-<NUM>-propene (HFO-1234ze)) have been disclosed to be effective refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentially damage the Earth's ozone layer, HFCs do not contain chlorine and thus pose no threat to the ozone layer.

Several methods of preparing hydrofluoroalkenes are known. For example, <CIT>) describes a method of making fluorine containing olefins by contacting hydrogen gas with fluorinated alcohols. Although this appears to be a relatively high-yield process, for commercial scale production the handling of hydrogen gas at high temperature raises difficult safety related questions. Also, the cost of producing hydrogen gas, such as building an on-site hydrogen plant, can be in many situations prohibitive.

<CIT>) describes a method of making fluorine containing olefins by pyrolysis of methyl chloride and tetrafluoroethylene or chlorodifluoromethane. This process is a relatively low yield process and a very large percentage of the organic starting material is converted in this process to unwanted and/or unimportant byproducts.

The preparation of HFO--1234yf from trifluoroacetylacetone and sulfur tetrafluoride has been described. See <NPL>). Also, <CIT>) discloses a process wherein tetrafluoroethylene is reacted with another fluorinated ethylene in the liquid phase to produce a polyfluoroolefin product.

<NPL> describes a study of atomic distances in polyfluorinated groups, including in propane and propene derivatives. The document describes the synthesis of a number of polyfluorinated propanes and propenes for this purpose, including a six-step process for the synthesis of CH<NUM>=CFCF<NUM> (HFO-1234yf) and which starts from CH<NUM>ClCHClCH<NUM>Cl.

<NPL> investigates the reaction kinetics of reactions involving halogenated alkanes, with a view to providing evidence for a novel rearrangement pathway. Decomposition of CF<NUM>ClCF<NUM>CH<NUM> and CF<NUM>ClCH<NUM>CD<NUM> resulted in decomposition products including CF<NUM>CF=CH<NUM> (HFO-1234yf).

Applicants have discovered a method for producing fluorinated organic compounds, as defined in the appended claims. The claims define reactions converting a compound of Formula (IB) to a compound of Formula (II) Of course, the subject-matter of the claims can be combined with steps involving combinations of compounds of Formula (I), including combinations of compounds of Formulas (IA), (IAA) and (IB) may be used, in accordance with the steps outlined below.

Following the present disclosure, the skilled person can convert a compound of Formula (IA) to a compound of Formula (IAA), then converting said Formula (IAA) compound to the Formula (IB) compound, and then converting the Formula (IB) to the Formula (II) compound. In certain more specific sequences of steps, the step of converting a compound of Formula (I) comprises providing at least one monchlortrifluorpropene in accordance with Formula (IAA), preferably CF<NUM>CCl=CH<NUM> (HFO-1233xf) and reacting said monchlortrifluorpropene under conditions effective to produce the compound of Formula (IB), namely CF<NUM>CFClCH<NUM> (HFC-244bb), which in turn is preferably exposed to reaction conditions effective to produce at least one compound in accordance with Formula (II), namely HFO-1234yf. In preferred embodiments said exposing step comprises conducting one or more of said reactions in a gas phase in the presence of a catalyst, preferably a metal-based catalyst. Examples of such preferred conversion steps are disclosed more fully hereinafter. Of course, it is contemplated that in the broad scope of the invention that any of the Formula (I) compounds may be converted, directly or indirectly, to the compound of Formula (II) in view of the teachings contained herein.

The claims therefore encompass exposing a compound of Formula (I), and preferably Formula (1A) or (IAA) to one or more sets of reaction conditions effective to produce the compound in accordance with Formula (II).

The preferred conversion step of the present invention is preferably carried out under conditions, including the use of one or more reactions, effective to provide a Formula (IB) conversion of at least about <NUM>%, more preferably at least about <NUM>%, and even more preferably at least about <NUM>%. In certain preferred embodiments the conversion is at least about <NUM>%, and more preferably at least about <NUM>%. Further in certain preferred embodiments, the step of converting the compound of Formula (IB) to produce a compound of Formula (II) is conducted under conditions effective to provide a Formula (II) yield of at least about <NUM>%, more preferably at least about <NUM>%, and more preferably at least about <NUM>%. In certain preferred embodiments a yield of about <NUM>% or greater is achieved.

One beneficial aspect of the present invention is that it enables the production of HFO-1234yf using relatively high conversion and high selectivity reactions. Furthermore, the present methods in certain preferred embodiments permit the production of HFO-1234yf, either directly or indirectly, from relatively attractive starting materials. For example, <NUM>-chloro, <NUM>,<NUM>,<NUM>,<NUM>-tetrafluoropropane is a compound that may in certain embodiments be an advantageous starting material because such products are relatively easy to handle.

In one preferred aspect covered by the claims, the conversion step comprises: (a) reacting a compound of Formula (IA), in a gas and/or liquid phase reaction in the presence of at least a first catalyst to produce at least one compound of Formula (IAA), such as a monochloro-trifluoro-propene, preferably HFO-1233xf; (b) reacting the at least one monochloro-trifluoro-propene compound, in a gas and/or liquid phase and preferably in the presence of at least a catalyst, preferably a second catalyst which is different than the first catalyst, to produce the compound of Formula (IB); and (c) reacting said compound of Formula (IB), in a gas and/or liquid phase, to produce HFO-1234yf. Each of the preferred reaction steps is described in detail below, with the headings being used for convenience but not necessarily by way of limitation.

One preferred reaction step may be described by those reactions in which the compound of Formula (IA) is fluorinated to produce a compound of Formula (IAA). In certain preferred embodiments, especially embodiments in which the compound of Formula (IA) comprises C(X)<NUM>=CClC(X)<NUM>, where each X is independently H or Cl, the present converting step comprises first reacting said compound(s) by fluorinating said compound(s), preferably with HF in a gas phase, to produce an HFO that is at least trifluorinated, such as HFO-1223xf. Preferably this gas phase reaction is at least partially catalyzed.

The preferred fluorination of the compound of Formula (IA) is preferably carried out under conditions effective to provide a Formula (IA) conversion of at least about <NUM>%, more preferably at least about <NUM>%, and even more preferably at least about <NUM>%. In certain preferred embodiments the conversion is at least about <NUM>%, and more preferably at least about <NUM>%. Further in certain preferred embodiments, the conversion of the compound of Formula (IA) comprises reacting such compound under conditions effective to produce at least one compound of Formula (IAA), such as monochlorotrifluoropropene (preferably CF<NUM>CCl=CH<NUM> (HFO-1233xf)) at a selectivity of at least about <NUM>%, more preferably at least about <NUM>%, more preferably at least about <NUM>%, and even more preferably at least about <NUM>%, with selectivities of about <NUM>% or greater being achieved in certain embodiments.

In general, it is possible that the fluorination reaction step can be carried out in the liquid phase or in the gas phase, or in a combination of gas and liquid phases, and it is contemplated that the reaction can be carried out batch wise, continuous, or a combination of these.

For embodiments in which the reaction comprises a liquid phase reaction, the reaction can be catalytic or non-catalytic. Preferably, a catalytic process is used. Lewis acid catalyst, such as metal-halide catalysts, including antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more of these, are preferred in certain embodiments. Metal chlorides and metal fluorides are particularly preferred. Examples of particularly preferred catalysts of this type include SbCl<NUM>, SbCl<NUM>, SbF<NUM>, SnCl<NUM>, TiCl<NUM>, FeCl<NUM> and combinations of two or more of these.

In preferred gas phase fluorination of Formula (IA) compounds, the reaction is at least partially a catalyzed reaction, and is preferably carried out on a continuous basis by introducing a stream containing the compound of Formula (I), preferably Formula (IA), into one or more reaction vessels, such as a tubular reactor. In certain preferred embodiments, the stream containing the compound of Formula (I), and preferably Formula (IA), is preheated to a temperature of from about80°C to about <NUM>, more preferably from about <NUM> to about <NUM>, and in certain embodiments preferably about <NUM>, and introduced into a reaction vessel (preferably a tube reactor), which is maintained at the desired temperature, preferably from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM> , even more preferably in certain embodiments from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, where it is preferably contacted with catalyst and fluorinating agent, such as HF.

Preferably the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.

Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable fluorination catalyst, with suitable means to ensure that the reaction mixture is maintained with the desired reaction temperature range.

Thus, it is contemplated that the fluorination reaction step may be preformed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein. However, it is preferred in certain embodiments that this reaction step comprise a gas phase reaction, preferably in the presence of catalyst, and even more preferably a chromium-based catalyst (such as Cr<NUM>O<NUM> catalyst), an iron-based catalyst (such as FeCl<NUM> on carbon (designated herein as FeCl<NUM>/C for convenience), and combinations of these. In preferred embodiments, the catalyst is a combination of the two aforementioned catalysts, where the reaction vessel contains in a first zone the chromium-based catalyst and in a second zone the iron-based catalyst. The temperature of the reaction in the chromium-based catalyst reaction is preferably kept at a temperature of from about <NUM> to about <NUM> and even more preferably from about <NUM> to about <NUM>. The temperature of the reaction in the iron-based catalyst reaction zone is preferably kept at a temperature of from about <NUM> to about <NUM> and even more preferably from about <NUM> to about <NUM>.

In general it is also contemplated that a wide variety of reaction pressures may be used for the fluorination reaction, depending again on relevant factors such as the specific catalyst being used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric or under vacuum and in certain preferred embodiments is from about1 to about <NUM> psia (from <NUM> to <NUM>,<NUM> kPa), and in certain embodiments from about <NUM> to about <NUM> psia (from <NUM> to <NUM> kPa).

In certain embodiments, an inert diluent gas, such as nitrogen, may be used in combination with the other reactor feed(s).

It is contemplated that the amount of catalyst use will vary depending on the particular parameters present in each embodiment.

The compound of Formula (IAA), preferably produced as described above, then is preferably subject to further fluorination reaction(s) to produce the compound of Formula (IB), HCFC-244bb. Preferably this gas phase reaction is at least partially catalyzed.

The fluorination of the compound of Formula (IAA) is preferably carried out under conditions effective to provide a Formula (IAA) conversion of at least about <NUM>%, more preferably at least about <NUM>%, and even more preferably at least about <NUM>%. Further in certain preferred embodiments, the conversion of the compound of Formula (IA) comprises reacting such compound under conditions effective to produce at least one monochlorotetrafluoropropane, including HCFC-244bb, at a selectivity of at least about <NUM>%, more preferably at least about <NUM>%, and even more preferably at least about <NUM>%, with selectivities of about <NUM>% or greater being achieved in certain embodiments.

In general, it is possible that this fluorination reaction step can be carried out in the liquid phase or in the gas phase, or in a combination of gas and liquid phases, and it is contemplated that the reaction can be carried out batch wise, continuous, or a combination of these.

In preferred gas phase fluorination of Formula (IAA) compounds, the reaction is at least partially a catalyzed reaction, and is preferably carried out on a continuous basis by introducing a stream containing the compound of Formula (IAA) into one or more reaction vessels, such as a tubular reactor. In certain preferred embodiments, the stream containing the compound of Formula (I), and preferably Formula (IAA), is preheated to a temperature of from about <NUM> to about <NUM>, and in certain embodiments preferably about <NUM>. In other embodiments, it is preferred that the stream containing the compound of Formula (I), and preferably Formula (IAA), is preheated to a temperature of from about <NUM> to about <NUM>, preferably about <NUM>. This steam, preferably after preheating, is then preferably introduced into a reaction vessel (preferably a tube reactor), which is maintained at the desired temperature, preferably from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, where it is preferably contacted with catalyst and fluorinating agent, such as HF.

Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable fluorination catalyst, with suitable means to ensure that the reaction mixture is maintained within about the desired reaction temperature range.

Thus, it is contemplated that the fluorination reaction step may be preformed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein. However, it is preferred in certain embodiments that this reaction step comprise a gas phase reaction, preferably in the presence of catalyst, and even more preferably an Sb-based catalyst, such as catalyst which is about 50wt% SbCls/C. Other catalysts which may be used include: from about <NUM> to about <NUM> wt% FeCl<NUM>/C; SbF<NUM>/C; about <NUM> wt% SnCl<NUM>/C; about <NUM> wt% TiCl<NUM>/C; and activated carbon. Preferably the catalyst comprises Cl<NUM> and HF pre-treated SbCls/C.

In general it is also contemplated that a wide variety of reaction pressures may be used for the fluorination reaction, depending again on relevant factors such as the specific catalyst being used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric or under vacuum and in certain preferred embodiments is from about <NUM> to about <NUM> psia (from <NUM> to <NUM>,<NUM> kPa), more preferably in certain embodiments from about <NUM> to about <NUM> psia (from <NUM> to <NUM> kPa).

The present claims may be described by those reactions in which the compound of Formula (IB) is dehydrohalogenated to produce a compound of Formula (II). In certain preferred embodiments, the stream containing the compound of Formula (IB), and preferably Formula (IBB) is preheated to a temperature of from about <NUM> to about <NUM>, preferably about <NUM>, and introduced into a reaction vessel, which is maintained at about the desired temperature, preferably from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, and more preferably in certain embodiments from about <NUM> to about <NUM>.

Preferably the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings. Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable dehydrohalogenation catalyst, with suitable means to heat the reaction mixture to about the desired reaction temperature.

Thus, it is contemplated that the dehydrohalogenation reaction step may be preformed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein. However, it is preferred in certain embodiments that this reaction step comprise a gas phase reaction, preferably in the presence of catalyst, and even more preferably a carbon- and/or metal-based catalyst, preferably activated carbon, a nickel-based catalyst (such as Ni-mesh) and combinations of these. Other catalysts and catalyst supports may be used, including palladium on carbon, palladium-based catalyst (including palladium on aluminum oxides), and it is expected that many other catalysts may be used depending on the requirements of particular embodiments in view of the teachings contained herein. Of course, two or more any of these catalysts, or other catalysts not named here, may be used in combination.

The gas phase dehydrohalogenation reaction may be conducted, for example, by introducing a gaseous form of a compound of Formula (IB) into a suitable reaction vessel or reactor. Preferably the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings. Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable dehydrohalogenation catalyst, with suitable means to heat the reaction mixture to about the desired reaction temperature.

While it is contemplated that a wide variety of reaction temperatures may be used, depending on relevant factors such as the catalyst being used and the most desired reaction product, it is generally preferred that the reaction temperature for the dehydrohalogentation step is from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, and even more preferably from about <NUM> to about <NUM>, and more preferably in certain embodiments from about <NUM> to about <NUM>.

In general it is also contemplated that a wide variety of reaction pressures may be used, depending again on relevant factors such as the specific catalyst being used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric or under vacuum, and in certain preferred embodiments is from about <NUM> to about <NUM> psia (from <NUM> to <NUM>,<NUM> kPa), and even more preferably in certain embodiments from about <NUM> to about <NUM> psia (from <NUM> to <NUM> kPa).

In certain embodiments, an inert diluent gas, such as nitrogen, may be used in combination with the other reactor feed(s). When such a diluent is used, it is generally preferred that the compound of Formula (I), preferably Formula (IB), comprise from about <NUM>% to greater than <NUM>% by weight based on the combined weight of diluent and Formula (I) compound.

Preferably in such dehydrofluorination embodiments as described in this section, the conversion of the Formula (IB) compound is at least about <NUM>%, more preferably at least about <NUM>%, and even more preferably at least about <NUM>%. Preferably in such embodiments, the selectivity to compound of Formula (II) is at least about <NUM>%, more preferably at least about <NUM>% and more preferably at least about <NUM>%.

Additional features of the present invention are provided in the following examples, which should not be construed as limiting the claims in any way.

About <NUM> grams of <NUM>,<NUM>,<NUM>-trichloropropane and about <NUM> grams Aliquat <NUM> were charged into a <NUM> liter glass vessel, equipped with TEFLON® shaft and stir blades, heated with internal TEFLON® coated copper coils and refrigerant/heating circulation bath and refrigerated condenser. The mixture was then heated to about <NUM> with medium speed agitation. At this temperature, about <NUM>,<NUM> grams of <NUM> wt% NaOH/H2O solution is added into the reactor from a separate container over a <NUM> hour period of time. The pH was kept at about <NUM>. After addition, the reaction progress was monitored by GC and GC/MS. The conversion of <NUM>,<NUM>,<NUM>-trichloropropane was about <NUM>% and the selectivity to CH<NUM>=CClCH<NUM>Cl was about <NUM>%. After the stipulated reaction time, the mixture was cooled and about <NUM> liters of distilled and ionized water was added into the mixture. The mixture was stirred for about <NUM> minutes and allowed to separate. The lower layer product (boiling point of about <NUM>) was drained and distilled to substantially isolate and purify product. The crude yield before distillation was about <NUM> grams (GC purity of about <NUM>%).

Chlorine was bubbled into about <NUM> of <NUM>,<NUM>-dichloropropene at about <NUM> to about <NUM> with the aid of ice bath cooling until a pale yellow color persisted for about <NUM> minutes. The crude product in an amount of about <NUM>, consisted of about <NUM> % CH<NUM>ClCCl<NUM>CH<NUM>Cl and about <NUM> % <NUM>,<NUM>-dichloropropene.

Five hundred grams of CH<NUM>ClCCl<NUM>CH<NUM>Cl was charged into a photoreactor. The jacket for the reactor as well as the jacket for the <NUM> W UV lamp were cooled to about <NUM> using a circulating cooling bath. A total of about <NUM> of chlorine was bubbled into the organic liquid over a period of about <NUM> hours. The crude product weighed about <NUM>. GC analysis indicated a conversion of about <NUM> % and selectivity for the desired HCCl<NUM>CCl<NUM>CH<NUM>Cl of about <NUM> %. Distillation provided HCCl<NUM>CCl<NUM>CH<NUM>Cl in <NUM> % purity.

Aliquat-<NUM>® (about <NUM>) and about <NUM> of HCCl<NUM>CCl<NUM>CH<NUM>Cl were stirred rapidly at room temperature while adding about <NUM> of <NUM> % aqueous NaOH over <NUM> minutes. Stirring was continued overnight before adding <NUM> water and allowing the phases to separate. The lower organic phase, in an amount of about <NUM>, was about <NUM> % pure CCl<NUM>=CClCH<NUM>Clby GC analysis (<NUM> % yield). Prior to fluorination, it was distilled (bp about <NUM> to about72 °C at about <NUM> Hg; <NUM> kPa) to remove any phase transfer catalyst. H NMR: δ <NUM> (s) ppm.

An <NUM>-inch long and <NUM>/<NUM>-inch diameter Monel pipe gas-phase reactor is charged with about <NUM> cc of a catalyst or a mixture of two catalysts. In case of a mixture, Cr<NUM>O<NUM> catalyst is kept at the bottom zone of the reactor at a constant temperature of about <NUM>-<NUM> and the other catalyst, such as FeCl<NUM>/C, is kept at the middle and the top zone of the reactor at a constant temperature of about <NUM> - <NUM>. The reactor is mounted inside a heater with three zones (top, middle, and bottom). The reactor temperature is read by custom-made-<NUM>-point thermocouples kept inside at the middle of the reactor. The bottom of the reactor is connected to a pre-heater, which is kept at <NUM> by electrical heating. The liquid-HF is fed from a cylinder into the pre-heater through a needle valve, liquid mass-flow meter, and a research control valve at a constant flow of about <NUM> to about <NUM> grams pre hour (g/h). The HF cylinder is kept at a constant pressure of <NUM> psig by applying anhydrous N<NUM> gas pressure into the cylinder head space. About <NUM> to about <NUM>/h of CCl<NUM>=CClCH<NUM>Cl is fed as a liquid through a dip tube from a cylinder under about <NUM> psig (<NUM> kPag) of N<NUM> pressure. The organic flowed from the dip tube to the preheater (kept at about <NUM>) through a needle valve, liquid mass-flow meter, and a research control valve at a constant flow of <NUM>-<NUM>/h. The organic is also fed as a gas while heating the cylinder containing organic at about <NUM>. The gas coming out of the cylinder is passed through a needle valve and a mass flow controller into the preheater. The organic line from the cylinder to the pre-heater is kept at about <NUM> by wrapping with constant temperature heat trace and electrical heating elements. All feed cylinders are mounted on scales to monitor their weight by difference. The catalysts are dried at the reaction temperature over a period of about <NUM> hours and then pretreated with about <NUM>/h of HF under atmospheric pressure over a period of about <NUM> hours and then under <NUM> psig HF pressure over another period of about <NUM> hours before contacting with organic feed containing CCl<NUM>=CClCH<NUM>Cl. The reactions are run at a constant reactor pressure of about <NUM> to about <NUM> psig (<NUM> to <NUM> kPag) by controlling the flow of reactor exit gases by another research control valve. The gases exiting reactor are analyzed by on-line GC and GC/MS connected through a hotbox valve arrangement to prevent condensation. The conversion of CCl<NUM>=CClCH<NUM>Cl is about <NUM> to about <NUM>% and the selectivity to 1233xf is about <NUM>% to about <NUM>%, respectively. The product is collected by flowing the reactor exit gases through a scrubber solution comprising about 20wt% to about <NUM> wt%. KOH in water and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N<NUM>. The product, 1233xf is then substantially isolated by distillation. The results are tabulated in Table <NUM>.

About <NUM> grams of HF, about <NUM> grams 1233xf, and about <NUM> grams SbCl<NUM> were charged into a <NUM>-L autoclave. The reaction mixture was stirred at a temperature of about <NUM> for about <NUM> hours under about <NUM> psig (<NUM> kPag) of pressure. After the reaction, the reactor was cooled to about <NUM> and about <NUM> water was then added slowly into the autoclave over a period of about <NUM>. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF<NUM>CFClCH<NUM> was about <NUM>% at a 1233xf conversion level of about <NUM>%. The other major by-products were CF<NUM>CF<NUM>CH<NUM> (<NUM>%), and an unidentified isomer of a C4 compound of the general formula, C<NUM>H<NUM>Cl<NUM>F<NUM> (<NUM>%).

About <NUM> grams HF, about <NUM> grams 1233xf, and about <NUM> grams SbCl<NUM> were charged into a <NUM>-L autoclave. The reaction mixture was stirred at <NUM> for about <NUM> hours under about <NUM> psig of pressure. After the reaction, the reactor was cooled to about <NUM> and then the overhead gas mixture was passed through a well dried KF, NaF, or Al<NUM>O<NUM> (<NUM>) packed column kept at about <NUM> to strip off HF from the gas stream. The gases coming out of the column are collected in a cylinder kept in dry ice (-<NUM>) bath. The yield of CF<NUM>CFClCH<NUM> was <NUM>% at a 1233xf conversion level of <NUM>%. The other major by-products were CF<NUM>CF<NUM>CH<NUM> (<NUM>%), and an unidentified isomer of a C4 compound of the general formula, C<NUM>H<NUM>Cl<NUM>F<NUM> (<NUM>%). The product, CF<NUM>CFClCH<NUM> was isolated by distillation with <NUM>% purity.

A <NUM>-inch (<NUM>/<NUM>-inch diameter) Monel tube gas phase reactor was charged with about <NUM> cc of a catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by a custom made <NUM>-point thermocouple kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about <NUM> by electrical heating. Organic (1233xf) was fed from a cylinder kept at <NUM> through a regulator, needle valve, and a gas mass-flow-meter. The organic line to the pre-heater was heat traced and kept at a constant temperature of about <NUM> by electrical heating to avoid condensation. N<NUM> was used as a diluent in some cases and fed from a cylinder through a regulator and a mass flow controller into the pre-heater. All feed cylinders were mounted on scales to monitor their weight by difference. The reactions were run at a constant reactor pressure of from about <NUM> to about <NUM> psig (<NUM> to <NUM> kPag) by controlling the flow of reactor exit gases by another research control valve. The gas mixtures exiting reactor was analyzed by on-line GC and GC/MS connected through a hotbox valve arrangements to prevent condensation. The conversion of 1233xf was from about <NUM>% to about <NUM>% and the selectivity to <NUM> isomer (CF<NUM>CFClCH<NUM>) was from about <NUM>% to about <NUM>% depending on the reaction conditions using <NUM> cc of <NUM> wt% SbCls/C as the catalyst at about <NUM> to about -<NUM> with a HF flow of about <NUM>/h and organic flow of about <NUM>/h. No CF<NUM>CF<NUM>CH<NUM> was observed under the reaction conditions. The catalyst is pretreated at first with <NUM>/h HF at about <NUM> for about <NUM> hours and then with about <NUM>/h HF and about <NUM> sccm of Cl<NUM> at about <NUM> for about <NUM> hours. After pre-treatment, about <NUM> sccm of N<NUM> is flowed over a period of about <NUM> minutes through the catalyst bed to sweep free chlorine from the catalyst surface prior to interacting with the organic feed (1233xf). Pretreatment is considered important to many embodiments of the invention. The products were collected by flowing the reactor exit gases through a <NUM>-<NUM> wt% aqueous KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N<NUM>. The products were then isolated by distillation. About <NUM> wt% SbCls/C, about <NUM> to about <NUM> wt% FeCl<NUM>/C, , <NUM> wt% SnCl<NUM>/C, and about <NUM> wt% TiCl<NUM>/C, using <NUM> different kind of activated carbon such as Shiro saga®, Calgon®, Norit®, and Aldrich® were used as the catalyst at from about <NUM> to about <NUM>. Among all the catalysts used for this reaction, Cl<NUM> and HF pre-treated SbCls/C was found to be generally preferred in terms of activity. The results using SbCl<NUM> as the catalyst are shown in Table <NUM>.

Reaction conditions: 1233xf flow, <NUM> sccm; HF flow <NUM>/h; pressure, <NUM>-<NUM> psig (<NUM>-<NUM> kPag); in <NUM>-<NUM> reactions Calgon® activated carbon is used as the catalyst support; catalyst, <NUM> cc. All catalysts are pre-treated with Cl<NUM> and HF prior to contacting with 1233xf.

A <NUM>-inch (<NUM>/<NUM>-inch diameter) Monel tube gas phase reactor was charged with <NUM> cc of catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by custom made <NUM>-point thermocouples kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about <NUM> by electrical heating. Organic (CF<NUM>CFClCH<NUM>) was fed from a cylinder kept at about <NUM> through a regulator, needle valve, and a gas mass-flow-meter. The organic line to the pre-heater was heat traced and kept at a constant temperature of from about <NUM> to about <NUM> by electrical heating to avoid condensation. The feed cylinder was mounted on scales to monitor their weight by difference. The reactions were run at a constant reactor pressure of from about <NUM> to about <NUM> psig (<NUM> to <NUM> kPag) by controlling the flow of reactor exit gases by another research control valve. The gas mixture exiting reactor was analyzed by on-line GC and GC/MS connected through a hotbox valve arrangement to prevent condensation. The conversion of CF<NUM>CFClCH<NUM> was almost <NUM>% and the selectivity to HFO-1234yf was from about <NUM>% to about <NUM>% depending on the reaction conditions. The products were collected by flowing the reactor exit gases through a about 20wt% to about <NUM> wt% of aquesous KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N<NUM>. The products were then isolated by distillation. Results are tabulated in T-able <NUM>.

Reaction conditions: pressure, <NUM>-<NUM> psig (<NUM>-<NUM> kPag); catalyst, <NUM> cc, A is NORIT® RFC <NUM>; B is Shiro-Saga® activated carbon; C is Aldrich® activated carbon; D is Calgon® activated carbon; activated carbon; E is <NUM> wt% Pd/C; F is <NUM> wt% Pt/C; G is Ni-mesh; Organic cylinder temperature-<NUM>; CF<NUM>CFClCH<NUM> (<NUM>) line to the preheater-<NUM>; Preheater, <NUM>; P-<NUM> psig (P-<NUM> kPag).

A <NUM>-inch long and <NUM>/<NUM>-inch diameter Monel pipe gas phase reactor was charged with <NUM> cc of a catalyst or a mixture of two catalysts. In case of a mixture, Cr<NUM>O<NUM> catalyst is kept at the bottom zone of the reactor at a substantially constant temperature of from about <NUM> to about <NUM> and the other catalyst, such as FeCl<NUM>/C is kept at the middle and the top zone of the reactor at a substantially constant temperature of from about <NUM> to about <NUM>. The reactor was mounted inside a heater with three zones (top, middle, and bottom). The reactor temperature was read by custom-made-<NUM>-point thermocouples kept inside at the middle of the reactor. The bottom of the reactor was connected to a pre-heater, which was kept at about <NUM> by electrical heating. The liquid-HF was fed from a cylinder into the pre-heater through a needle valve, liquid mass-flow meter, and a research control valve at a substantially constant flow of from about <NUM> to about <NUM>/h. The HF cylinder was kept at a substantially constant pressure of about <NUM> psig (<NUM> kPag) by applying anhydrous N<NUM> gas pressure into the cylinder head space. A feed rate of from about <NUM>/h to about <NUM>/h of CCl<NUM>CCl=CH<NUM> was fed as a liquid through a dip tube from a cylinder under about <NUM> psig (<NUM> kPag) of N<NUM> pressure. The organic was flown from the dip tube to the pre-heater (kept at about <NUM>) through needle valve, liquid mass-flow meter, and a research control valve at a substantially constant flow of from about <NUM> to about <NUM>/h. The organic is also fed as a gas while heating the cylinder containing organic at about <NUM>. The gas effluent from the cylinder is passed through a needle valve and a mass flow controller into the pre-heater. The organic line from the cylinder to the pre-heater was kept at about <NUM> by wrapping with constant temperature heat trace and electrical heating elements. All feed cylinders were mounted on scales to monitor their weight by difference. The catalysts were dried at the reaction temperature over a period of about <NUM> hours and then pretreated with about <NUM>/h of HF under atmospheric pressure over a <NUM> hour period and then under about <NUM> psig (<NUM> kPag) HF pressure over a <NUM> hour period before contacting with organic feed, CCl<NUM>CCl=CH<NUM>. The reactions were run at a substantially constant reactor pressure ranging from about <NUM> to about <NUM> psig (<NUM> to <NUM> kPag) by controlling the flow of reactor exit gases by another research control valve. Those gases exiting reactor were analyzed by on-line GC and GC/MS connected through a hotbox valve arrangements to prevent condensation. The conversion of CCl<NUM>CCl=CH<NUM> was in a range of from about <NUM>% to about <NUM>% and the selectivity to CF<NUM>CCl=CH<NUM> (1233xf) was about <NUM>%. The effluent contained in addition HFO-1243zf in an amount of about <NUM>%, <NUM>-isomer in an amount of about <NUM>%, and <NUM> in an amount of about <NUM>%, and an unidentified byproduct. The product was collected by flowing the reactor exit gases through a <NUM>-<NUM> wt% aq. KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N<NUM>. The product, 1233xf was then substantially isolated by distillation. Using only Cr<NUM>O<NUM> catalyst, a selectivity of about <NUM>% to 1233xf at a conversion level of about <NUM>% was achieved.

About <NUM> grams HF, about <NUM> grams CCl<NUM>CCl=CH<NUM>, and about <NUM> grams SbCl<NUM> were charged into a <NUM>-L autoclave. The reaction mixture was stirred at about <NUM> for about <NUM> hours under about <NUM> psig (<NUM> kPag) of pressure. After the reaction, the reactor was cooled to about40°C and about <NUM> water was then added slowly into the autoclave over a period of about <NUM>. After complete addition of water under stirring, the reactor was cooled to about room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF<NUM>CFClCH<NUM> was about <NUM>% at a CCl<NUM>CCl=CH<NUM> conversion level of about <NUM>%. The other major by-products were CF<NUM>CF<NUM>CH<NUM> (<NUM>%), and an unidentified isomer of a C4 compound of the general formula, C<NUM>H<NUM>Cl<NUM>F<NUM> (<NUM>%).

About <NUM> grams HF, about <NUM> grams CCl<NUM>CCl=CH<NUM>, and about <NUM> grams SbCl<NUM> were charged into a <NUM>-L autoclave. The reaction mixture was stirred at about <NUM> for about <NUM> hours under about <NUM> psig (<NUM> kPag) of pressure. After the reaction, the reactor was cooled to about <NUM> and about <NUM> water was then added slowly into the autoclave over a period of about <NUM> minutes. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF<NUM>CFClCH<NUM> was about <NUM>% at a CCl<NUM>CCl=CH<NUM> conversion level of about <NUM>%. The other major by-products were CF<NUM>CF<NUM>CH<NUM> (about <NUM>%), and an unidentified isomer of a C4 compound of the general formula, C<NUM>H<NUM>Cl<NUM>F<NUM> (about <NUM>%).

About <NUM> grams HF, about <NUM> grams CCl<NUM>CCl=CH<NUM>, and about <NUM> grams SbCl5 were charged into a <NUM>-L autoclave. The reaction mixture was stirred at about <NUM> for about <NUM> hours under about <NUM> psig (<NUM> kPag) of pressure. After the reaction, the reactor was cooled to about <NUM> and about <NUM> water was then added slowly into the autoclave over a period of about <NUM>. After complete addition of water under stirring, the reactor was cooled to about room temperature and then the overhead gases were transferred to another collecting cylinder. The major products were CF<NUM>CF<NUM>CH<NUM> (about <NUM>%) and CF<NUM>CFClCH<NUM> (about <NUM>%) at a CCl<NUM>CCl=CH<NUM> conversion level of about <NUM>%. The other major by-products were and unidentified isomer of a C4 compound of the general formula, C<NUM>H<NUM>Cl<NUM>F<NUM> (<NUM>%) and tar.

About <NUM> grams HF, about <NUM> grams CCl<NUM>CCl=CH<NUM>, and about <NUM> SbCl<NUM> were charged into a <NUM>-L autoclave. The reaction mixture was stirred at about <NUM> for about <NUM> hours under about <NUM> psig (<NUM> kPag) of pressure. After the reaction, the reactor was cooled to about <NUM> and about <NUM> water was then added slowly into the autoclave over a period of about <NUM> minutes. After complete addition of water under stirring, the reactor was cooled to about room temperature and then the overhead gases were transferred to another collecting cylinder. The major products were CF<NUM>CF<NUM>CH<NUM> (about <NUM>%) and CF<NUM>CFClCH<NUM> (about <NUM>%) at a CCl<NUM>CCl=CH<NUM> conversion level of about <NUM>%. The other major by-products were and unidentified isomer of a C4 compound of the general formula, C<NUM>H<NUM>Cl<NUM>F<NUM> (about <NUM>%) and tar.

A <NUM>-inch (<NUM>/<NUM>-inch diameter) Monel tube gas phase reactor was charged with <NUM> cc of a catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by custom made <NUM>-point thermocouples kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about <NUM> by electrical heating. Organic material (245cb) was fed from a cylinder kept at about <NUM> through a regulator, needle valve, and a gas mass-flow-meter. The organic line to the pre-heater was heat traced and kept at a substantially constant temperature in a range of from about <NUM> to about <NUM> by electrical heating to avoid condensation. The feed cylinder was mounted on a scale to monitor its weight by difference. The reactions were run at a substantially constant reactor pressure of from about <NUM> to about <NUM> psig (<NUM> to <NUM> kPag) by controlling the flow of reactor exit gases by another research control valve. The gas mixtures exiting reactor was analyzed by on-line GC and GC/MS connected through a hotbox valve arrangements to prevent condensation. The conversion of 245cb was in the range of from about <NUM>% to about <NUM>% and the selectivity to 1234yf was in the range of from about <NUM>% 5o about <NUM>% depending on the reaction conditions. The products were collected by flowing the reactor exit gases through a <NUM>-<NUM>-wt% of aq. KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N<NUM>. The products were then substantially isolated by distillation. Results are tabulated in Table <NUM>.

Reaction conditions: pressure, <NUM>-<NUM> psig (<NUM>-<NUM> kPag); catalyst, <NUM> cc, A is NORIT® RFC <NUM>; B is Shiro-Saga® activated carbon; C is Aldrich® activated carbon; D is Calgon® activated carbon; E is <NUM> wt% Pd/C; F is <NUM> wt% Pt/C; G is Ni-mesh; Organic cylinder temperature is about <NUM>; CF<NUM>CF<NUM>CH<NUM> (245cb) line to the preheater is maintained at about <NUM>OC; preheater temperature is maintained at about <NUM>; N<NUM> flow is not used; pressure is maintained at about <NUM> psig (<NUM> kPag).

Claim 1:
A method for producing fluorinated organic compounds comprising converting at least one compound of Formula (IB)

        CF<NUM>CFClCH<NUM>     (IB)

[HCFC-244bb]
to at least one compound of Formula (II)

        CF<NUM>CF=CH<NUM>     (II)

[HFO-1234yf],
wherein the converting step is carried out in a vessel comprising Hastelloy, Inconel, Monel and/or a fluoropolymer lining.