FIELD

[0001] The present invention relates to processes for the production of chlorinated alkanes, and in particular, to processes for the production of tri-, tetra- and pentachlorinated alkanes.

BACKGROUND

[0002] Hydrofluorocarbon (HFC) products are widely utilized in many applications, including refrigeration, air conditioning, foam expansion, and as propellants for aerosol products including medical aerosol devices. Although HFC's have proven to be more climate friendly than the chlorofluorocarbon and hydrochlorofluorocarbon products that they replaced, it has now been discovered that they exhibit an appreciable global warming potential (GWP).

[0003] The search for more acceptable alternatives to current fiuorocarbon products has led to the emergence of hydrofluoroolefm (HFO) products. Relative to their predecessors, FIFOs are expected to exert less impact on the atmosphere in the form of a lesser, or no, detrimental impact on the ozone layer and their lower GWP as compared to HFC's. Advantageously, HFO's also exhibit low fiammabiiity and low toxicity.

[0004] As the environmental, and thus, economic importance of HFO's has developed, so has the demand for precursors utilized in their production. Many desirable HFO compounds, e.g., such as 2,3,3 ,3-tetrafluoroprop- 1 -ene or 1,3,3,3- tetrafluoroprop-I-ene, may typically be produced utilizing feedstocks of chlorocarbons, and in particular, highly chlorinated alkanes, e.g., tri-, tetra- and pentachioroalkanes.

[0005] Unfortunately, these higher chlorides have proven difficult to manufacture using acceptable process conditions and in commercially acceptable regioselectivities and yields. For example, conventional processes for the production of trichloropropane (such as those disclosed in US Patent No. 2,1 19,484 and US Patent No. 4,051,182) provide unacceptable selectivity to the desired trichloropropane isomer, make use of suboptimal chlorinating agents, and/or require the use of expensive catalyst systems and/or initiators. Suboptimal selectivity to the trichloropropane often unfortunately leads to an even further reduction in selectivity to the desired higher chlorinated alkanes, e.g., tetra- and pentachiorinated alkanes.

[0006] It would thus be desirable to provide improved processes for the production of chlorocarbon precursors useful as feedstocks in the synthesis of refrigerants and other commercial products. More particularly, such processes would provide an improvement over the current state of the art if they provided a higher regioselectivity relative to conventional methods, made use of optimal chlorinating agents and/or made use of less expensive catalyst systems and/or initiators.

BRIEF DESCRIPTION

[0007] The present invention provides efficient processes for the production of chlorinated alkanes. More particularly, the processes make use of a trichiormated alkane to produce tetra- and pentachJoroalkanes with high selectivity. In some embodiments, the processes advantageously make use of 1 , 1 ,2- trichloropropane, which, in some embodiments, may be produced in situ via the ionic chlorination of 1,2-dichloropropane. The desired starting material is initially dehydrochlorinated and as a result, selectivity of the process to, e.g., 1 ,1,1,2,2-pentachloropropane, is enhanced over conventional processes that utilize only chlorination steps.

[0008] In one aspect, the present invention provides a process for the production of tetra- and 'or pentachiorinated alkanes from one or more trichiormated alkanes. The triehlorinated alkane comprises from 3-6 carbon atoms, or from 3-5 carbon atoms, or from 3-4 carbon atoms, or 3 carbon atoms and desirably comprises vicinal chlorine atoms. In some embodiments, the trichiormated alkane comprises 1, 1,2-trichloropropane.

[0009] The process comprises first dehydrochlorinating the one or more triehlorinated alkanes, rather than subjecting the same to a first chlorination step. This initial dehydrochlorination is desirably conducted in the presence of caustic, rather than catalytically. The triehlorinated alkane may advantageously be produced in situ by the ionic chlorination of a dichlorinated alkane, e.g., 1,2-dichloropropane. The product stream of the dehydrochlorination of the triehlorinated alkane is subjected to sequential chlorination and/or further dehydrochlorination steps. In some embodiments, all steps after the initial dehydrochlorination may be chlorination steps, or the process may comprise a combination, such as an alternating combination, of chlorination and dehydrochlorination steps. [0010] Any or all of the chlorinaiion steps within the process may be conducted in the presence of an ionic elilorination caialyst. Suitable ionic chlorinaiion catalysts include Lewis acids, such as, aluminum chloride (AICI ₃ ), iodine (¾), ferric chloride (FeClj), sulphur, antimony pentachloride, boron trichloride, one or more lanthanum halides, one or more metal inflates, or combinations of these. In some embodiments, any ionic chlormaiions may desirably be carried out in the presence of aluminum chloride. Chlorine, suifuryl chloride (S0 ₂ C1 ₂ ) or combinations of these, may be used as chlorinating agents in any, some or all chlorinaiion steps. In some embodiments, one or more chlormaiions may be conducted in the presence of a solvent, such as, e.g., methylene chloride, carbon tetrachloride, and/or 1 , 1 ,2,3-tetraehloropropane,

[001 1] The first and/or any further dehydrochlorinaiions used in the process are desirably conducted in the liquid phase, and may be conducted in the presence of one or more chemical bases, caustic, potassium hydroxide, calcium hydroxide or a combination of these. Phase transfer catalysts may also be used and suitable examples of these include quaternary ammonium and quaternary phosphonium salts.

[0012] The liquid phase dehydrochlorination of the trichloroalkane is highly selective and as a result, the number of separation or purification steps used in the process can be reduced as compared to conventional processes for the production of chlorinated alkanes that chlorinate this intermediate. In some embodiments, no purification steps may be necessary between dehydrochlorination and chiorination steps.

[0013] Any chlorinated alkane may be produced by the process, but due to its importance as a feedstock in other processes for the production of refrigerants, the production of 1 ,1,1,2,2-pentachloropropane is contemplated in some embodiments.

DESCRIPTION OF THE FIGURES

[0014] FIG. 1 shows a schematic representation of a process according to one embodiment;

[0015] FIG. 2 shows a schematic representation of a process according to another embodiment; and

[0016] FIG. 3 shows a schematic representation of a process according to another embodiment.

DETAILED DESCRIPTION

[0017] The present specification provides certain definitions and methods to better define the present invention and to guide those of ordinary skill in the art in the practice of the present invention. Provision, or lack of the provision, of a definition for a particular term or phrase is not meant to imply any particular importance, or lack thereof. Rather, and unless otherwise noted, terms are to be understood according to conventional usage by those of ordinary skill in the relevant art.

[0018] The terms "first", "second", and the like, as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Also, the terms "a" and "an" do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item, and the terms "front", "back", "bottom", and/or "top", unless otherwise noted, are merely used for convenience of description, and are not limited to any one position or spatial orientation.

[0019] If ranges are disclosed, the endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of "up to 25 wt.%, or, more specifically, 5 wt.% to 20 wt.%," is inclusive of the endpoints and ail intermediate values of the ranges of "5 wt.% to 25 wt.%," etc.). As used herein, percent (%) conversion is meant to indicate change in molar or mass flow of reactant in a reactor in ratio to the incoming flow, while percent (%) selectivity means the change in molar flow rate of product in a reactor in ratio to the change of molar flow rate of a reactant.

[0020] Reference throughout the specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection wiih an embodiment is included in at least one embodiment. Thus, the appearance of the phrases "in one embodiment" or "in an embodiment" in various places throughout the specification is not necessarily referring to the same embodiment. Further, the particular features, structures or characteristics may be combined in any suitable manner in one or more embodiments.

[0021] The present invention provides efficient processes for the production of chlorinated alkanes. The present processes comprise reacting one or more trichlorinated alkanes to provide tetra- and/or pentachlorinated alkanes, with high regioselectivity. More particularly, the present processes fsrst dehydrochlorinate the triehloroalkane, rather than first chlorinating this material, as may have been done in conventional processes. Selectivity to the corresponding 1 , 1 -dichloroalkene is enhanced, and further reaction steps lead to, e.g., 1,1,1 ,2,2-pentachloropropane with enhanced selectivity as well.

[0022] Any trichlorinated aikane having from 3-6 carbon atoms, or from 3-5 carbon atoms, or from 3-4 carbon atoms, or 3 atoms, can be utilized as a starting material in the process. The trichlorinated aikane desirably comprises vicinal chlorine atoms, i.e., chlorine atoms present on adjacent carbon atoms. The use of vicinal trichlorinated alkanes with two chlorine atoms in the first carbon is thought to contribute to the regioselectivity provided by the process, and such trichlorinated alkanes are preferred in some embodiments. For example, in those embodiments wherein the starting material comprises the vicinal trichioropropane 1,1 ,2-trichloropropane, regioselectivity to l,l, l,2~tetrachloropropane and/or 1,1 ,1 ,2,2-pentachloropropane can be seen.

[002.3] In some embodiments, the 1 , 1 ,2 -trichioropropane may be produced in situ, e.g., via the sonic chlorination of 1,2-dichloropropan.e. The use of 1 ,2-dichloropropane as a feedstock for the production of 1, 1 ,2-trichloropropane used in the process is advantageous, since it may be available at low cost due to its production as a by-product in many chiorohydrin processes.

[0024] The tetra-, and/or pentachlorinated aikane produced by the process will depend upon the trichlorinated aikane used as a starting material. And so, the processes can be used to produce alkanes comprising from 3-6 carbon atoms, or from 3-5 carbon atoms, or from 3-4 carbon atoms, in some embodiments, and due to the commercial significance of tetra- and pentachlorinated propanes and butanes, the use of one or more di- and/or trichlorinated propanes and butanes as starting materials may be preferred. In some embodiments, 1,1,2- trichloropropane is utilized as a starting material to produce 1,1,1 ,2-tetrachloropropane and/or 1,1,1, 2,2 -pentachloropropane at high selectivity.

[0025] One or more of the dehydrochlorination steps of the present process may be conducted in the presence of a liquid caustic. Although vapor phase dehydrochlorinations could be used, liquid phase dehydrochlorination reactions provide higher selectivity to the desired intermediates. Liquid phase dehydrochlorinations also provide the opportunity for cost savings since evaporation of reactants is not required. The lower reaction temperatures used in liquid phase reactions may also result in slower fouling rates than those observed in connection with the higher temperature gas phase reactions, and so reactor lifetimes may also be optimized when at least one liquid phase dehydrochlormation is utilized.

[0026] Many chemical bases are known in the art to be useful for liquid dehydrochlorinations, and any of these can be used. For example, suitable bases include, but are not limited to, alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, calcium hydroxide; alkali metal carbonates such as sodium carbonate; lithium, rubidium, and cesium or combinations of these. Phase transfer catalysts such as quaternary ammonium and quaternary phosphonium salts (e.g. benzyitrimethylammonium chloride or hexadeeyltrihutylphosphonium bromide) can also be added to improve the dehydrohalogenation reaction rate with these chemical bases.

[0027] The product from the dehydrochlorination of the trichlorinated alkane is subsequently subjected to a series of chlorination and/or dehydrochlorination steps. All remaining steps of the process may be chlorination steps, or less than all, or only one. Desirably, the chlorination steps used in the process are conducted in the presence of ionic chlorination catalysts, which further enhance the specificity of the process.

[0028] The specificity of the process is further enhanced by the use of a Lewis acid as an ionic chlorination catalyst. The use of ionic chlorination catalysts in the present process is particularly advantageous since they can promote dehydrochlorination and catalyze chlorination reactions within the same reactor. That is, ionic chlorination catalysts remove a chlorine and hydrogen from adjacent carbon atoms, the adjacent carbon atoms form a double bond, and HC1 is released. A chlorine molecule is then added back, replacing the double bond, to provide a more highly chlorinated alkane. [0029] Ionic chlormation catalysts are well known to those of ordinary skill in the art and any of these may be used in (he present process. Exemplar ionic chlormation catalysts include, but are not limited to, aluminum chloride, ferric chloride (FeCU) and other iron containing compounds, iodine, sulfur, antimony pentachlori.de (SbCls), boron trichloride (BC¾), lanthanum halides, metal inflates, and combinations thereof. Of these, aluminum chloride and ferric chloride are Lewis acids, and so, their use in (he process may be preferred in some embodiments.

[0030] Any or all of the catalysts utilized in the process can be provided either in bulk or in connection with a substrate, such as activated carbon, graphite, silica, alumina, zeolites, fluorinated graphite and fluorinated alumina. Whatever the desired catalyst (if any), or format thereof, those of ordinary skill in the art are well aware of meihods of determining the appropriate format and method of introduction thereof. For example, many catalysts are typically introduced into the reactor zone as a separate feed, or in solution with other reactants.

[0031 ] The amount of any ionic chlormation and'Or dehydrochiorination catalyst utilized will depend upon the particular catalyst chosen as well as the other reaction conditions. Generally speaking, in those embodiments of the invention wherein the utilization of a catalyst is desired, enough of the catalyst should be utilized to provide some improvement to reaction process conditions (e.g., a reduction in required temperature) or realized products, but yet not be more than will provide any additional benefit, if only for reasons of economic practicality,

[0032] For purposes of illustration only then, it is expected, that useful concentrations of the ionic chlormation catalyst will range from 0,001% to 20% by weight, or from 0.01 % to 10%, or from 0.1% to 5 wi.%, inclusive of ail subranges therebetween. If a dehydroelilorination caialyst is utilized for one or more dehydrochiorination steps, useful concentrations may range from 0.01 wt.% to 5 wt.%, or from 0,05 wt.% to 2 wt.% at temperatures of from 70°C to 200°C. If a phase transfer catalyst is utilized, useful concentrations may typically be less than 0.1 wt%, or less than lOOOppm. Relative concentrations of each catalyst are given relative to the feed of reactant, including any- recycled reactants and/or intermediates to the reaction vessel. If a chemical base is utilized for one or more dehydrochlorinations, useful concentrations of these will range from 0.01 to 20 grmole/L, or from 0.1 grmole/L to i 5grmole/L, or from 1 grmole/L to 10 grmole/L, inclusive of all subranges therebetween.

[0033] The chlorination steps of the process may be carried out using any chlorination agent, and several of these are known in the art. For example, suitable chlorination agents include, but are not limited to chlorine, and/or sulfuryl chloride (S0 ₂ C] ₂ ). Combinations of chlorinating agents may also be used. Either or both Cl ₂ and sulfuryl chloride may be particularly effective when aided by the use of the aforementioned ionic chlorination catalysts. In some embodiments, one or more chlorination steps may be conducted in the presence of a solvent, such as, e.g., methylene chloride, carbon tetrachloride, and 1 , 1 ,2,3- tetrachloropropane, or combinations of these.

[0034] The reaction conditions under which the process is carried out in liquid phase and thus are advantageously low intensity. That is, low temperatures, e.g., of less than 10Q°C, or less than 90°C, or less than 80°C or less than 70'C, or less than 60°C, or less than 50°C, or even as low as 40°C may be utilized and the desired selectivities to the tri-, terra-, and/or pentachloroalkanes yet be realized. In some embodiments, temperatures of from 40°C to 70°C, or 55°C to 65°C may be utilized. Similarly, ambient pressure is suitable for carrying out the process, or pressures within 250, or 200, or 150, or 100, or 50, or 40, or 30, or 20, or even l Opsi, of ambient are suitable. Reactor occupancy may also be minimized with the desired selectivities yet seen - for example, reactor occupancy times of less than 20 hours, or less than 15 hours, or less than 10 hours, or less than 5 hours, or less than 4, 3, 2, or even 1 hour, are possible. The reactor may be any suitable liquid phase reactor, such as a batch, semi-batch or continuous stirred tank aittoclave reactor with an internal cooling coil. A shell and multitube exchanger followed by vapor liquid disengagement tank or vessel can also be used.

[0035] In additional embodiments, one or more reaction conditions of the process may be optimized, in order to provide even further advantages, i.e., improvements in selectivity, conversion or production of reaction by-products. In certain embodiments, multiple reaction conditions are optimized and even further improvements in selectivity, conversion and production of reaction by-products produced can be seen.

[0036] Reaction conditions of the process that may be optimized include any reaction condition conveniently adjusted, e.g., that may be adjusted via utilization of equipment and/or materials already present in the manufacturing footprint, or thai may be obtained at low resource cost. Examples of such conditions may include, but are not limited to, adjustments to temperature, pressure, flow rates, molar ratios of reactants, etc.

[0037] That being said, the particular conditions employed at each step described herein are not critical, and are readily determined by those of ordinary skill in the art. What is important is that a feedsiream comprising a trichloroalkane having from 3-6 carbon atoms and further comprising at least two vicinal chlorine atoms is first subjected to a dehydrochlorination step, rather than a chiorination step. Those of ordinary skill in the art will readily be able to determine suitable equipment for each step, as well as the particular conditions at which the chiorination, dehydrochlorination, separation, drying, and isomerization steps may be conducted.

[0038] In one exemplary process, 1 ,1,2-trichioropropane is dehydrochlorinated, using caustic, to provide 1, 1-dichloropropene. The 1 ,1,2-tri.chj.oropropane may be provided in situ, e.g., via the reaction of 1,2-dichloropropane (PDC) with sulfuryl chloride in the presence of aluminum chloride at a temperature of from 55°C to 65°C, ambient pressure and a reactor occupancy of less than one hour.

[0039] The 1,1 -dichloropropene is then chlorinated to provide 1 ,1, 1,2-tetraehloropropane, which is then dehydrochlorinated using caustic or eatalytically, to provide 1, 1,2- trichioropropene. The 1,1 ,2-trichloropropene is then chlorinated to provide 1, 1 ,1,2,2- pentachloropropane. In other embodiments, the 1, 1 ,1,2-tetraehloropropane ma be chlorinated, and in such embodiments, all steps after the initial dehydrochlorination of the 1 , 1 ,2-trichi.oropropane would be chiorination steps.

[0040] A schematic illustration of one embodiment of such a process is shown in FIG. 1. As shown in FIG. 1 , process 100 incorporates dehydroclilormation reactor 1 12, drying unit 1 14, chiorination reactor 1 16, and separation units 1 18 and 120.

[0041] In operation of process 100, l , l,2-trich3oropropane and recycled 1, 1 ,1 ,2- tetraehloropropane are fed to dehydrochlorination reactor 1 12, wherein they are dehydrochlorinated using caustic to produce 1,1-dichloropropene and 1 , 1,2-trichloropropene, respectively. The product stream from dehydrochlorination reactor 1 12 is then dried in drying unit 1 14 and fed to chiorination reactor 1 16. [0042] The dried product stream from dehydrochlorination reactor, comprising 1 , 1 - dichloropropene and 1, 1 ,2-trichloropropene, is chlorinated in chlorination reactor 1 16 to provide 1 , 1 , 1 ,2-tetrachloropropane and 1 , 1 , 1 ,2,2-pentachloropropane respectively. Any excess CI? and any HCI byproduct may be vented off an overhead stream and provided to a purification unit (not shown) for recovery of the HCI and CI?.. Any recovered CI? may be recycled to chlorination reactor 1 16, if desired.

[0043] The product stream from chlorination reactor 1 16, comprising 1 , 1 , 1 ,2- tetrachloropropane and 1 , 1 , 1 ,2,2-pentachloropropane, is fed to separation unit 1 18. Separation unit 1 1 8 is operated at conditions effective to provide unreacted di- and trichioropropenes and 1 , 1 , 1 ,2-tetrachloropropane as an overhead stream, which may be recycled to dehydrochlorination reactor 1 12, if desired. The bottom stream of separation unit, comprising 1 ,1 ,1 ,2,2-pentaehloropropane, is fed to separation unit 120 which is operated at conditions effective to provide 1 , 1 , 1 ,2,2-pentachloropropane as an overhead stream. The 1,1,1 ,2,2-pentachloropropane may optionally be recovered with a solvent, e.g., such as 1 , 1 ,2,3-tetrachloropropane, other pentachloropropane isomers or the hexachloropropane byproduct. Further purification methods, such as crystallization, may be used to purify the 1 , 1 , 1 ,2,2-pentachloropropane, if desired.

[0044] A schematic illustration of another embodiment of the process is shown in FIG. 2. More particularly, in process 200, the 1 , 1 ,2-trichloropropane is provided in situ, via the chlorination of 1 ,2-dichIoropropane. Process 200 thus includes chlorination reactor 202, HCI recovery unit 204, quench/drying unit 206, and separation units 208 and 21 0, in addition to the components used in process 100, identified with similar reference numerals incremented by 100.

[0045] In operation, 1 ,2-dichloropropane is fed to chlorination reactor 202 and chlorinated in the presence of a catalytic aluminum chloride to produce 1 , 1 ,2-trichloropropane and anhydrous HCI as byproduct. The HCi and excess chlorine is fed to HCI purification unit 204 where anhydrous HCI is purified and taken as the overhead stream. The bottom stream comprising CI _? is then recycled back to reactor 202. The bottom product stream of chlorination reactor 202, comprising 1 , 1 ,2-trichloropropane, is quenched to remove aluminum chloride in the aqueous phase. The organic product is dried in drying unit 206 and the dried stream provided to separation unit 208. [0046] Separation unit 208 is operated at conditions effective to provide 1 ,2- dichloropropane as an overhead stream and a bottom stream comprising 1, 1,2- trichloropropane and 1 ,2,3-trichloropropane. The overhead stream from separation unit may be recycled to chlorination reactor 202, while the bottoms stream is provided to separation unit 210. Separation unit is operated at conditions effective to provide 1 , 1 ,2-triehloropropane as an overhead stream and 1 ,2,3-trichloropropane as a bottoms stream. The bottoms stream may be appropriately disposed of, while the overhead stream, consisting of substantially pure 1 , i ,2-trichioropropane is provided to dehydroehlorination reactor 212. The rest of process 200 proceeds as described in FIG. 1.

[0047] A schematic illustration of another embodiment of the process is shown in FIG. 3. More particularly, process 300 makes use of 1 , 1 -dichloropropene as a starting material. Process 300 thus includes chlorination reactor 302, HQ recovery unit 304, quench/drying unit 306, and separation units 318 and 320.

[0048] in operation of process 300, 1,1 -dichloropropene is fed to chlorination reactor 302 and chlorinated in the presence of a catalytic amount of aluminum chloride to produce 1,1,1 ,2,2-pentachloropropane, 1,1,1 ,2-tetrachloropropane intermediate, and anhydrous HQ as a byproduct. The HC1 and excess chlorine is fed to HC1 purification unit 304 where anhydrous HQ is purified and taken as the overhead stream. The bottom stream comprising Cl ₂ is then recycled back to reactor 302. The bottom product stream of chlorination reactor 302, comprising 1 ,1 , 1,2,2-pentachloropropane, 1 ,1 ,1 ,2-tetrachloropropane, and heavies is quenched to remove aluminum chloride in the aqueous phase. The organic product is dried in drying unit 306 and the dried stream provided to separation unit 318.

[0049] Separation unit 318 is operated at conditions effective to provide unreacted 1 ,1- dichloropropene and 1,1,1 ,2-tetrachloropropane as an overhead stream and a bottom stream comprising 1,1,1 ,2,2-pentachloropropane and heavies. The overhead stream from separation unit 318 may be recycled to chlorination reactor 302 via the HQ recover '- unit 304, while the bottoms stream is provided to separation unit 320. Separation unit 320 is operated at conditions effective to provide 1, 1,1,2,2-pentachloropropane as an overhead stream and heavies, i.e. 1,1 ,1 ,2,2,3-hexachloropropane, as a bottom stream.

[0050] Some embodiments of the invention will now be described in detail in the following examples. [0051 ] Example 1. Preparation of 1 , 1 -dichloropropene from 1 , i ,2-trichloropropane

[0052] A round-bottom flask is charged with 1 , 1 ,2-trichloropropane (40.7 g) and benzyl trimethyiammonium chloride (1.97 g) and heated to 70 °C and then charged with aqueous caustic solution (5. ON, 60 niL). After 4 hours, the solution is cooled to ambient temperature. The phases are separated and the aqueous phase is extracted with an equal volume of methylene chloride. The organic phases are combined and dried over magnesium sulfate. The dried crude solution contains 1 , 1 ,-dichloropropene as determined by GC and NMR spectroscopic analysis (2.4.5 g, 80.6% yield) dissolved in methylene chloride. Ή NMR ( CDC! ;. 500 MHz): ppm - 5.90 (q, 1H), 1.76 (d, 3H).

[0053] Example 2. Preparation of 1 , 1 , 1 ,2-Tetrachloropropane from 1 , -dichloropropene

[0054] A l OOmL Parr vessel is charged with the dried crude product mixture from Example 1 containing 1 , 1 -dichloropropene (24.5 g) and sealed. The reactor is pressurized to 125 psig and heated to 50 ^C C while Cl ₂ (30% v/v in N?, 200 seem) is fed to the reactor. The chlorine flow is halted after 90 mmuies and the reactor is returned to ambient temperature and pressure. The crude reaction mixture is analyzed by GC to indicate that the mixture is composed of 84.0% l , l , l ,2-tetrach3oropropane, 6.6% 1, 1 , 1 ,2,2-pentachloropropane, 6.0% 1 , 1 -dichloropropene, and a balance of unidentified low-level byproducts. The crude reaction mixture is neutralized with aqueous sodium bicarbonate to remove residual dissolved chlorine and dried over magnesium sulfate. The crude material is purified by vacuum distillation (24 torr, 59 °C) to give 1 , 1,1 ,2-tetrachloropropane ( 19.7 g, 48.9% yield). ^J H NMR (CDCI ₃ , 500 MHz): ppm = 4.60 (q, 1H), 1.85 (d, 3H). ¹³ C NMR (CDCI ₃ , 500 MHz): ppm = 1 01.67, 68.46, 21.46. GC-MS: M ^÷ = 145, 109, 83, 75, 63.

[0055 ] Example 3. Preparation of 1 , 1 ,2 -trichloropropene from 1 , 1 , 1 ,2-tetrachloropropane

[0056] A round-bottom flask is charged with 1, 1 , 1 ,2-tetrachloropropane (18.0 g) and benzyl trimethyiammonium chloride (1.84 g) and heated to 70 °C and then charged with aqueous caustic solution (5. ON, 20 mL). The solution is stirred for 24 hours and then cooled to ambient temperature. The phases are separated and the aqueous phase is extracted with an equal volume of methylene chloride. The organic phases are combined and dried over magnesium sulfate and filtered. The dried crude liquid is concentrated under reduced pressure and then analyzed by Ή NMR and GC and determined to contain 1 , 1 ,2- trichloropropene as the major product. ^! H NMR (CDCI ₃ , 500 MHz): ppm = 2.28 (s, 3H). This product mixture is used without further purification in the subsequent Example 4.

[0057] Example 4. Preparation of 1,1, 1, 2,2 -pentachloropropane from 1,1,2- trichloropropene

[0058] This crude product mixture from Example 3 is dried with molecular sieves and then charged to a 1 OOmL Parr vessel and sealed. The reactor is pressurized to 125 psig with Cl ₂ (30% v/v in N ₂ , 200 seem) and heated to 50 °C while Cl ₂ (30% v/v in N ₂ , 200 seem) is fed to the reactor. The chlorine flow is halted after 90 minutes and the reactor is returned to ambient temperature and pressure. The crude reaction mixture is neutralized with aqueous sodium bicarbonate and then dried over magnesium sulfate. The crude material is purified by evaporation of the solvent to give 1,1 ,1 ,2,2-pentachloropropane (3.8g, 21.5% yield) as a white solid. Ή NMR (CDCI ₃ , 500 MHz): ppm = 2.51 (s). ⁱ³ C NMR (CDCI ₃ , 500 MHz): ppm = 104.81 , 95.02, 33.1 1 . GC-MS: JVT = 181 , 143, 97. Although selectivity in this particular example is high, the yield is believed low due to the volatility of the product, which may be ameliorated with handling techniques specific to accommodating this volatility.

[0059] Example 5. Preparation of 1, 1 ,1 ,2,2-pentachloropropane from 1 ,1 -dichloropropene

[0060] A 3 OOmL Parr vessel is charged with the dried crude product mixture from Example 1 containing 1 , 1 -dichloropropene (3.4 g), methylene chloride (50mL), and aluminum chloride (O.lg) and sealed. The reactor is pressurized to 125 psig with Cl ₂ (30% v/v in N2, 200 seem) and heated to 70 °C while Cl ₂ (30% v/v in N ₂ , 50 seem) is fed to the reactor. The reaction mixture was analyzed by GC after 20 minutes and found to be comprised of 68.2% 1,1,1,2,2-pentachloropropane and 24.2% 1,1, 1,2,2,3-hexachloropropane with a balance of low-level chlorinated propanes.

[0061] Example 6. Preparation of 1,1, 1,2,2-pentachloropropane from 1, 1, 1,2- tetrachl oropropane

[0062] A 300mL Parr vessel is charged with 1,1,1 ,2-tetrachloropropane (2.94 g), methylene chloride (50mL) ferric chloride (0.13 g) and sealed. The reactor is pressurized to 125 psig with CI? (30% v/v in N _? , 200 seem) and heated to 70 °C while CI? (30% v/v in N ₂ , 50 seem) is fed to the reactor. The reaction mixture was analyzed by GC after 60 minutes to be comprised of 77.9% unreacted 1,1,1 ,2-tetrachloropropane starting material, 13.4% 1,1,1 ,2,2-pentachloropropane, and 4.3% l _; l,l ,2,2,3-hexachloropropane with a balance of low level chlorinated propanes.