PROCESS FOR RECOVERING 2,3,5,6-TETRACHLOROPYRIDINE FROM MIXTURES OF CHLORINATED PYRIDINES

Abstract: Substantially pure 2,3,5,6-tetrachloropyridine is recovered from a mixture of chlorinated pyridines containing 2,3,5,6-tetrachloropyridine, at least one of 2,3,4,5-tetrachloropyridine and 2,3,4,6-tetrachloropyridine and certain other chlorinated pyridines in an improved process which comprises (a) reacting, by contacting, a first such mixture of chlorinated pyridines with chlorine in the presence of a strong Lewis acid catalyst thereby to obtain a second mixture consisting essentially of 2,3,5,6-tetrachloropyridine and pentachloropyridine, and (b) recovering the 2,3,5,6-tetrachloropyridine from the second mixture, especially by fractional distillation. The reaction is normally conducted at a temperature of from 150°C to 300°C by pressurizing chlorine into a molten mixture of the chlorinated pyridines and maintaining such conditions until substantially all of the isomers have been converted to the symmetrical tetrachloropyridine or pentachloropyridine.

Description: "PROCESS FOR RECOVERING 2,3,5,6-TETRACHLOROPYRIDINE" This invention is directed to a process for recoveing substantially pure 2,315,6-tetrachloropyridine from mixtures of chlorinated pyridines. Highly chlorinated pyridine compounds, such as 2,3,5,6-tetrachloropyridlne, are known to be useful as pesticides or as intermediates for the preparation of other compounds having pesticidal properties. The various processes used to prepare chlorinated pyridines and especially 2,3,5,6-tetrachloropyridine have generally resulted in producing product mixes containing many chlorinated compounds including 2,3,4,5- and 2,3,4,6tetrachloropyridine, the two position isomers of the desired 2,3,5,6-tetrachloropyridine. It has been particularly difficult to separate 2,3,5,6-tetrachloropyridine from its two position isomers by conventional economical techniques such as distillation since the boiling points of these three materials are so close. It has therefore been necessary to resort to more costly, difficult and time-consuming procedures of selective crystallization and multistage and/or multiplate distillation. It has now been found that both 2,3,4,5-and 2,3,4,6-tetrachloropyridine are converted to pentachloropyridine at a much more rapid rate than 2,3,5,6 -tetrachloropyridine when they are chlorinated in the presence of a Lewis acid catalyst. Because of this difference in reaction rates, both 2,3,4,5-and 2,3,4,6 -tetrachloropyridine can be substantially converted to pentachloropyridine prior to substantial conversion of any 2,3,5,6-tetrachloropyridine which might be in admixture with the above isomers. The separation of 2,3,5, 6-tetrachloropyridine from pentachloropyridine is a rather easy procedure. Nore particularly, it has been found that substantially pure 2,3,5,6-tetrachloropyridine can be recovered from a first mixture containing initially 2,3,5,6-tetrachloropyridine, pentachloropyridine and at least one of 2, 3,4,5-tetrachloropyridine and 2,3,4,6 -tetrachloropyridine and no more than minor amounts, if any, of monochloropyridires, 3,5-dichloropyridine, 2,3,5,-trichloropyridine and 2,3,6-trichloropyridine and no other chloropyridine compounds. The present process comprises the steps of (a) reacting by contacting a first mixture of chlorinated pyridines with chlorine in the presence of a Lewis acid catalystthereby to obtain a second mixture of chlorinated pyridines consisting essentially of 2,3,5,6-tetrachloropyridine and pentachloropyridine, and (b) recovering the 2,3,5,6 -tetrachloropyridine from the second mixture. There are several commercially significant advantages of the present process over prior art procedures. First, the process of the invention results in a mixture consisting essentially of symmetrical tetrachloropyridine and pentachloropyridine; which is easily separated by conventional techniques (e.g., distillation). Second, pentachloropyridine is known to be a starting material for use in reductive reactions leading to tetrachloropyridines and the pentachloropyridine produced in the present process can be recovered and recycled to generate additional symmetrical tetrachloropyridine. Third, the present process is a straightforward facile process which obviates the need of expensive, sophisticated distillation apparatus or selective crystallization apparatus to recover symmetrical tetrachloropyridine from a mixture of close boiling position isomers of tetrachloropyridine or a mixture of polychlorinated pyridines. Significant capital savings as well as reduced operating expenditures are thus substantially achieved. These and other advantages will be readily apparent to those skilled in the art of manufacturing symmetrical tetrachloropyridine. Normally, commercial routes of producing symmetrical tetrachloropyridine result in a mixture of tri-, tetra- and pentachloropyridines. All of these mixtures normally melt at elevated temperatures (e.g., 90"C-1250C) and the molten mixture is used as the reaction medium in the present process. Examples of Lewis acids which can be employed in the present process include, o-phosphoric acid, boron trifluoride, aluminum chloride, aluminum oxychloride, chromium trichloride, ferric chloride, ruthenium chloride, and the corresponding bromides, aluminum oxide, ferric oxide, and ferric acetylacetonate. The catalyst, which is normally a solid can be employed as such (unsupported) or the catalyst can be supported on a carrier. Representative carriers include, for example, molecular sieves, gamma alumina, silica, silica gel, silica-alumina, and graphite. It has been observed that Lewis acids in which the metal or cationic portion of the compound has an oxidation state of plus 3 or more (usually +3 or +5) as the predominant configuration (e.g. Fe +3) are normally catalysts in the present process. Such compounds are considered to be strong Lewis acids. The preferred compounds are Lewis acids which are covalent metal halides and the most preferred catalysts are ferric chloride and aluminum chloride. The covalent metal halides can be used per se (which is the desired embodiment) or they can be generated in situ by adding the metal to the reaction mixture. For example, iron or aluminum can be added to the reaction mixture and ferric chloride and aluminum chloride will be generated in situ. The catalysts are used in amounts of up Lo 10 weight percent, based on the weight of the chloropyridine reactant mixture. Preferably, however, the catalyst is included in amounts of from 0.05 to 0.5 weight percent. The catalysts are quite effective and generally the lesser amount is satisfactory and facilitates removal of the catalyst at the end of the reaction. The reaction may be conducted by contacting the chloropyridine mixtures with chlorine in the presence of the catalyst by a slurry technique or by contacting the mixture with the catalyst over a static bed or a fluidized bed of the catalyst. The process may be conducted in a batchwise manner, a continuous manner or a cyclic batch manner in which the pentachloropyridine and symmetrical tetrachloropyridine are removed leaving the catalyst in a distillation residue or in a quantity of the reaction mixture in the reaction vessel and fresh reactants then merely introduced into the reaction vessel. In this manner, the catalyst is recovered and re-used. The reaction is conducted at elevated temperatures normally above the melting point of the chloropyridine mixture. Desirable rates of reaction have been achieved at temperatures of from 1500C to 3000C although somewhat higher or lower temperatures could be used, if desired. Preferred rates of reaction have been observed at temperatures of from 2000C to 2500C. The reaction can be conducted at atmospheric or superatmospheric pressure (e.g., 15-75 psig (2-6 atm) or higher) but superatmospheric pressures are normally desired. As is well known, chlorine is a gas and the solubility of chlorine in the chloropyridine mixtures is enhanced by use OI superatmospheric pressures. This superatmospheric pressure may be provided with chlorine or an inert gas (e.g., nitrogen or HC1) but is normally provided by chlorine gas. The process may be conducted in the presence of an inert solvent, if desired, but is preferably conducted neat. Suitable inert solvents include chlorinated hydrocarbons such as for example methyl chloroform, and carbon tetrachloride. The following examples will further illustrate the invention. Experimental The following experiments were conducted in a glass reaction vessel at atmospheric pressure and in a high pressure stainless steel autoclave at elevated pressures. The analysis of the reaction mixture and end products was accomplished by vapor phase chromatography. Examples 1-5 A mixture of chlorinated pyridines was charged to an externally heated glass reactor vessel equipped with a mechanical stirrer, reflux condenser and a glass sparger and the mixture heated until molten. The mixture of chloropyridines included some or all of the following compounds in various amounts: 3,5-Dichloropyridine, 2,3,5-trichloropyridine, 2,3,6 -trichloropyridine, pentachloropyridine and the three -position isomers of tetrachloropyridine. Ferric chloride was added to this molten-mixture with stirring. The molten mixture was then heated to approximately 2000C and chlorine was sparged into the reaction mixture. The course of the reaction was followed by taking analytical samples of the reaction mixture from time to time and following the disappearance of the undesirable isomers in the gas chromatograph. The data from these examples (runs) are summarized in Table I below. TABLE I Run Run Catalyst Catalyst Time Component Analysis Feed (wt %) No. Type wt % (Hrs) 3,5 Di 2,3,5 Tri 2,3,6 Tri Tetras Penta 1 None - 4 - - - 73.37 25.36 2 FeCl3 0.05 6 - - - 73.43 25.21 3 FeCl3 0.50 3 - - - 73.71 24.61 4 FeCl3 3.21 2 - - - 73.22 25.66 5 FeCl3 2.94 5 0.096 2.834 0.662 67.23 23.19 (continued) TABLE I (Continued) Run Catalyst % Conversion No. Type 3,5 Di 2,3,5 Tri 2,3,6 Tri 2,3,4,5 2,3,4,6 2,3,5,6 1 None - - - 6.04 7.87 5.22 2 FeCl3 - - - 17.47 56.59 4.37 3 FeCl3 - - - 12.66 100 7.06 4 FeCl3 - - - 65.81 100 13.49 5(a) FeCl3 100 77.98 100 -143 97.4 -0.1 (a) In this Run, 3,5-dichloropyridine was converted to 2,3,5-trichloropyridine which was converted to both 2,3,4,5- and 2,3,5,6-tetrachloropyridine and pentachloropyridine. 2,3,6-Trichloropyridine was converted to 2,3,5,6-tetrachloropyridine and pentachloropyridine. Additional reaction time would increase pentachloropyridine production and give substantially complete chlorination of 2,3,5-trichloropyridine, 2,3,4,5- and 2,3,4,6-tetrachloropyridine. TABLE I (Continued) Tetrachloropyridine Isomer Distribution in Percent of Total Tetra's Run Catalyst Initial Final No. Type 2,3,4,5 2,3,4,6 2,3,5,6 2,3,4,5 2,3,4,6 2,3,5,6 1 None 0.126 2.673 97.20 0.125 2.600 97.27 2 FeCl3 0.121 2.664 97.21 0.106 1.228 98.67 3 FeCl3 0.115 2.621 97.26 0.111 - 98.87 4 FeCl3 0.123 2.699 97.18 0.050 - 99.95 5 FeCl3 0.140 2.86 97.00 0.350 0.076 99.57 The negative numbers under "percent conversion" in Table I means that that particular isomer was being produced during the course of the reaction. The positive numbers, on the other hand, indicate that that particular isomer was being consumed during the course of the reaction and leading to reduced amounts of that material in the final product. The reader will note the very desirable ratio of symmetrical tetrachloropyridine to the other position isomers thereof in the final product. No di- or trichloropyridines were observed in the final product (except Run 5 as noted above). Final product thus consisted essentially of pentachloropyridine and symmetrical tetrachloropyridine. This mixture was resolved into pentachloropyridine and symmetrical tetrachloropyridine (along with any minor amounts of tetrachloropyridine ppsition isomers) by distillation under reduced pressure. The dashes in Table I means that none of that particular isomer was present in either the feed or the final reaction product. Examples 6-20 In this series of experiments, a mixture of tetra- and pentachioropyridines was charged to a high pressure stainless steel autoclave, the reaction mixture melted, and the catalyst indicated in Table II added. The autoclave was subsequently sealed, heated to reaction temperature, and pressurized with a pad of chlorine entering through a top valve. Once pressurized, chlorine gas was then continuously sparged through the reaction mixture with stirring and analytical samples taken during the course of the reaction. The data from these experiments are summarized in Table II. TABLE II REACTANT RUN CONDITIONS CONDITIONS Catalyst Wt. % of Catalyst Time Temp. Press. Exp. Type to Total Tetra's Hrs. C psig (atm) 1 FeCl3 0.05 1.75 206 55 (4.74) 2 FeCl3 0.50 1.75 202 51 (4.46) 3 FeCl3 5.03 0.75 201 49 (4.33) 4 FeCl3 0.50 1.25 242 25 (2.7) 5 FeCl3 0.50 3.0 241 52 (4.53) 6 FeCl3 0.50 0.75 238 74 (6.03) 7 FeCl3 0.5 4.5 160 51 (4.46) 8 FeCl3 0.50 2.5 180 53 (4.6) 9 FeCl3 0.50 1.75 212 50 (4.4) 10 FeCl3 0.50 3.0 241 52 (4.53) TABLE II (Continued) % TETRACHLOROPYRIDINE ISOMER DISTRIBUTION OF TOTAL TETRA'S IN FEED Exp. 2,3,4,5 2,3,4,6 2,3,5,6 1 0.136 2.676 97.19 2 0.127 2.630 97.243 3 0.045 1.68 98.28 4 0.027 1.794 98.18 5 0.418 20.21 79.37 6 0.037 1.768 98.11 7 0.061 2.13 97.81 8 0.033 2.40 97.60 9 0.069 1.93 97.99 10 0.418 20.21 79.37 TABLE II (Continued) REACTANT RUN CONDITIONS CONDITIONS Catalyst Wt. % of Catalyst Time Temp. Press. Exp. Type to Total Tetra's Hrs. C psig (atm) 11 FeCl3 0.05 7.0 180 49 (4.33) 12 FeCl3 0.05 7.0 200 25 (2.7) 13 FeCl3 0.05 4.0 241 52 (4.53) 14 AlCl3 0.43 1.50 220 50 (4.4) 15 Al2O3 1.43 2.50 240 51 (4.46) 16 Fe2O3 5.02 3.0 243 54 (4.67) 17 #Fe 0.49 3.0 243 51 (4.46) 18 SbCl5 0.90 1.25 222 50 (4.4) 19 ZnCl2 0.42 4.0 207 51 (4.46) 20 None - 4.0 203 50 (4.4) # Steel Wool TABLE II (Continued) % TETRACHLOROPYRIDINE ISOMER DISTRIBUTION OF TOTAL TETRA'S IN FEED Exp. 2,3,4,5 2,3,4,6 2,3,5,6 11 0.030 2.06 97.91 12 0.093 4.904 95.00 13 0.418 20.21 79.37 14 0.070 2.01 97.92 15 0.030 1.745 98.22 16 0.034 1.814 98.15 17 0.180 12.69 87.13 18 0.069 1.930 97.99 19 0.127 2.630 97.24 20 0.136 2.676 97.19 # Steel Wool TABLE II (Continued) REACTANT RUN CONDITIONS CONDITIONS Catalyst Wt. % of Catalyst Time Temp. Press. Exp. Type to Total Tetra's Hrs. C psig (atm) 21 AlOCl 0.987 2 220 25 (2.7) 22 AlCl3 on 13 X molecular sieve 0.421 1 220 25 (2.7) 23 9.9% AlCl3 on Silica gel 0.610 2 220 25 (2.7) 24 AlCl3 on &alpha; alumina 0.109 2 220 25 (2.7) 25 22.9% AlCl3 on Graphite 1.130 4 220 25 (2.7) 26 Filtrol Grade 13 Clay (a) 2.050 2 220 25 (2.7) 27 Nafion# Powder 501 (b) 7.843 4 219 25 (2.7) 28 SK-500 Molecular Seive (c) 7.843 5 220 25 (2.7) TABLE II (Continued) % TETRACHLOROPYRIDINE ISOMER DISTRIBUTION OF TOTAL TETRA'S IN FEED Exp. 2,3,4,5 2,3,4,6 2,3,5,6 21 0.088 8.948 90.96 22 0.141 9.634 90.23 23 0.098 9.421 90.48 24 0.129 8.695 91.16 25 0.067 6.658 93.28 26 0.150 9.615 90.24 27 0.120 9.553 90.34 28 0.112 9.616 90.27 TABLE II (Continued) REACTANT RUN CONDITIONS CONDITIONS Catalyst Wt. % of Catalyst Time Temp. Press. Exp. Type to Total Tetra's Hrs. C psig (atm) 29 H3PO4 (solid) 8.07 8 220 25 (2.7) 30 Filtrol Grade 62 Clay (a) calcined 7.843 5 220 25 (2.7) 31 Filtrol Grade 62 Clay (a) uncalcined 8.667 9 220 25 (2.7) (a) Filtrol grades 13 and 62 are proprietary materials of the Filtrol Corporation and are acid activated clays with high Lewis acid properties. (b) Nafion# 501 is a proprietary material of E.I. DuPont DeNemours & Company and is a perfluorosulfonic acid resin. This material is a commercial acid catalyst. (c) SK-500 is a proprietary material of Union Carbide Corporation. The material is an acid catalyst and is a crystalline aluminoslicate derived from Type Y molecular siever. TABLE II (Continued) % TETRACHLOROPYRIDINE ISOMER DISTRIBUTION OF TOTAL TETRA'S IN FEED Exp. 2,3,4,5 2,3,4,6 2,3,5,6 29 0.115 8.330 91.55 30 0.210 9.537 90.24 31 0.231 8.952 90.82 TABLE II (Continued) % TETRACHLOROPYRIDINE ISOMER % TETRACHLOROPYRIDINE DISTRIBUTION IN PRODUCT ISOMER CONVERSION Exp. 2,3,4,5 2,3,4,6 2,3,5,6 2,3,4,5 2,3,4,6 2,3,5,6 1 0.082 0.706 99.21 40.71 74.13 0.0 2 0.093 0.0 99.91 30.38 100.0 2.32 3 0.047 0.0 99.95 5.14 100.0 7.63 4 0.015 0.0 99.99 51.62 100.0 10.11 5 0.375 0.028 99.60 37.35 99.90 11.55 6 0.031 0.0 99.97 21.31 100.0 2.93 7 0.047 0.27 99.68 16.67 86.28 -8 0.050 0.020 99.93 -- 99.16 -9 0.058 0.0 99.94 20.08 100.0 3.03 10 0.375 0.028 99.60 37.35 99.90 11.55 11 0.04 0.195 99.76 -- 90.76 0.74 TABLE II (Continued) % TETRACHLOROPYRIDINE ISOMER % TETRACHLOROPYRIDINE DISTRIBUTION IN PRODUCT ISOMER CONVERSION Exp. 2,3,4,5 2,3,4,6 2,3,5,6 2,3,4,5 2,3,4,6 2,3,5,6 12 0.086 0.027 99.89 10.51 99.47 -13 0.261 0.010 99.73 57.87 99.96 14.39 14 0.062 0.0 99.94 17.11 100.0 4.35 15 0.019 0.063 99.91 37.63 98.34 0.16 16 0.017 -- 99.98 72.38 100.0 42.72 17 0.140 -- 99.85 53.71 97.67 13.52 18 0.060 0.899 99.04 16.01 55.01 2.38 19 0.109 3.166 96.78 13.08 -19.37 -0.8 20 0.107 2.896 96.99 22.22 - 6.99 1.34 21 0.177 0.055 99.75 -75.4 99.5 4.33 TABLE II (Continued) % TETRACHLOROPYRIDINE ISOMER % TETRACHLOROPYRIDINE DISTRIBUTION IN PRODUCT ISOMER CONVERSION Exp. 2,3,4,5 2,3,4,6 2,3,5,6 2,3,4,5 2,3,4,6 2,3,5,6 22 0.148 0.118 99.73 10.42 98.95 5.65 23 0.154 0.011 99.84 -34.7 99.9 5.40 24 0.204 0.059 99.74 -42.1 99.4 1.74 25 0.155 0.118 99.73 -122.1 98.30 -2.64 26 0.165 0.182 99.65 5.84 98.38 5.46 27 0.144 0.096 99.76 -25.74 99.10 1.70 28 0.127 0.70 99.75 1.73 93.69 4.24 29 0.148 0.218 99.63 -15.3 97.7 2.47 30 0.233 0.005 99.76 2.34 97.85 2.695 31 0.232 0.076 99.69 5.88 99.20 -2.86 The data in Table II can be viewed in sections: Experiments 1-3 show the effect of catalyst concentration; experiments 4-6 show the effect of pressure on the reaction; experiments 7-13 show the effect of temperature on the reaction; experiments 14-31 show the effect of various catalysts in addition to ferric chloride; and experiments 19 and 20 also show the effect of a weak Lewis acid (i.e., zinc chloride) or no catalyst at all. The negative numbers under "percent conversion" in Table II means that that particular isomer was being produced during the course of the reaction while the positive numbers, on the other hand, indicate that that particular isomer was being consumed during the course of the reaction and leading to reduced amounts of that material in the final product. In the above Runs, the small amount of 3,5-dichloropyridine present (not listed in the feed makeup) was converted to 2,3,5-trichloropyridine which in turn was converted to 2,3,4,5-, and 2,3,5,6-tetrachloropyridine and pentachloropyridine. The 2,3, 6-trichloropyridine (also not listed as part of the feed makeup) was converted to 2,3,5, 6-tetrachloropyridine and pentachloropyridine. Additional reaction time would increase pentachloropyridine production and give substantially complete chlorination of 2,3, 5-trichloropyridine, 2,3,4,5- and 2,3,4,6-tetrachloropyridine. The dashes in Table II means that none of that particular isomer was present in the final reaction product. These reaction mixtures were likewise resolved into pentachloropyridine and symmetrical tetrachloropyridine using distillative techniques. The above examples show that the present process is very effective in resolving a complex mixture of chlorinated pyridines into a mixture consisting essentially of pentachloropyridine and symmetrical tetrachloropyridine which are easily resolved by conventional techniques. Various catalysts have been used in these examples and various other process parameters have been illustrated. Other catalysts and/or process parameters can be varied according to the above teaching.

Claims: Claims: 1. A process for recovering substantially pure 2,3,5,6-tetrachloropyridine from a first mixture containing initially 2,3,4,6-tetrachloropyridine, pentachloropyridine and at least one of 2,3,4,5-tetrachloropyridine and 2,3,4,6-tetrachloropyridine and no more than minor amounts, if any, of monochloropyridines, 3,5-dichloropyridine, 2,3, 5-trichioropyridine and 2,3,6-trichloropyridine and no other chloropyridine compounds which process comprises the steps of (a) reacting, by contacting, the first mixture of chlorinated pyridines, in liquid phase under atmospheric or superatmospheric pressure, with chlorine in the presence of a Lewis acid catalyst thereby to obtain a second mixture of chlorinated pyridines consisting essentially of 2,3,5,6tetrachloropyridine and pentachloropyridine, and (b) recovering the 2,3,5,6-tetrachloropyridine from the second mixture. 2. A process as claimed in claim 1 wherein the Lewis acid is a covalent metal chloride. 3. A process as claimed in claim 2 wherein the Lewis acid is ferric chloride or aluminum chloride. 4. A process as claimed in any one of the preceding claims wherein the Lewis acid is present in an amount of up to 10 weight percent, based on the weight of the first mixture of chlorinated pyridines. 5. A process as claimed in claim 4 wherein the Lewis acid is present in an amount of from 0.05 to 0.5 weight percent, based on the weight of the first mixture of chlorinated pyridines. 6. A process as claimed in any one of the preceding claims wherein the reaction is effected at a temperature of from 1500 to 300or. 7. A process as claimed in claim 6 wherein the raction is effected at a temperature orf from 200 to 250 C. 8. A process as claimed in any one of the preceding claims wherein the reaction is carried out at superatmospheric pressure in the absence of a solvent. 9. A process as claimed iii any one of the preceding claims wherein the 2,3,5,6-tetrachloropyridine is recovered in step (b) by fractional distillation.

Inventors: DEAN, NORMAN LEROY, PERETTIE, DONALD JOSEPH
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1979
Main classification: C07D213
IPC codes: C07D213