Patent Publication Number: US-6342630-B1

Title: Chemical process

Description:
The present invention relates to a process for the purification of diphenyl ether compounds which are useful as herbicides or as intermediates in the synthesis of herbicides. In particular, it relates to a process for obtaining particular nitrated isomers of diphenyl ether compounds from mixtures containing other nitrated isomers. 
     Diphenyl ether herbicides are known, for example from EP-A-0022610 which relates to herbicides of the formula:                    
     wherein X and Y may be H, F Cl, Br, CF 3 , OCF 2 CHZ 2  (Z=Cl, Br, F), OCH 3 , CN, CO 2 R (R=lower alkyl), C 6 H 5 , O-alkyl, NO 2  or SO 2  lower alkyl; 
     and also describes a process for making these compounds by nitrating a compound of the formula:                    
     wherein X and Y are as defined above. 
     Suggested nitrating agents for this reaction include mixtures of nitric and sulphuric acids and the recommended reaction solvent is dichloromethane. The nitration process is said to give a yield of 75.4% but no details are given of the purity of the product or the presence of other nitrated isomers. 
     U.S. Pat. No. 4,031,131 describes similar compounds to the above which are prepared in a similar manner. Suggested nitrating agents include potassium nitrate or mixed nitric and sulphuric acids and the reaction is carried out in dichloromethane. An extremely high yield (&gt;95%) is claimed for the nitration reaction but, again, there are no details given about the purity of the product. Nitration reactions using mixed nitric and sulphuric acids may also be carried out in the presence of acetic anhydride. 
     EP-A-0003416 and EP-A-0274194 both relate to the synthesis of herbicidal compounds of the formula:                    
     wherein 
     R 1  is alkyl optionally substituted with fluorine or optionally substituted phenyl; 
     R 3  is H, F, Cl, Br, I alkyl, trifluoromethyl or CN; 
     R 4  is H, F, Cl, Br, I or trifluoromethyl; 
     R 5  is F, Cl, Br, I or trifluoromethyl; and 
     R 6  is H or C 1 -C 4  alkyl. 
     In EP-A-0003416, these compounds may be obtained by nitrating the corresponding carboxylic acid or carboxamide and then converting to the sulphonamide or by nitrating the sulphonamide itself. A nitration reaction is described in Example 7 where the solvent is 1,2-dichloroethane and the nitrating agent is a mixture of potassium nitrate and concentrated sulphuric acid. 
     EP-A-0274194 relates, in particular, to a process for the nitration of compounds of the formula:                    
     The nitration reaction is said to be carried out using a conventional nitrating agent such as concentrated nitric acid or sodium nitrate or mixtures of these with sulphuric acid. The reaction solvent is one which is resistant to nitration and examples of such solvents are said to include halogenated solvents such as dichloromethane, dichloroethane, dichloropropane, chlorofluorocarbons and aromatic solvents such as nitrobenzene. 
     However, none of these methods are particularly satisfactory for use on an industrial scale because they all have the common problem that the reaction yields a mixture of the required product and other nitrated isomers. Nitrated isomers of diphenyl ether compounds are often extremely difficult to separate from one another and the quantity of other isomers is often too high for the final product to fulfil the requirements of the regulatory authorities for herbicides. The problem tends to be further exacerbated if the nitrated product is an intermediate in the synthesis of a herbicide rather than the required herbicide itself because the mixture of nitrated compounds means that larger quantities of other reagents must be used than would be necessary if the nitrated isomers could be separated satisfactorily. It is therefore important to ensure that the nitration process produces a product mixture containing the highest possible proportion of the desired isomer. 
     The problem of obtaining mixtures of isomers from the nitration process was recognised by the authors of GB-A-2103214 who describe a process in which a compound of the formula:                    
     wherein each of 
     X 1 , X 2 , and X 3 , is H, fluorine, chlorine, bromine, CF 3 , O CF 2 ,CHZ 2  (where Z is F, Cl or Br), OCF 3 , CN, COOR (R is lower alkyl), phenyl, lower alkoxy or NO 2 R and at least one of X 1 , X 2 , and X 3  is other than hydrogen; and 
     Y is COOR or carboxy; 
     is nitrated to give a product of the formula:                    
     wherein X 1 , X 2 , X 3  and Y are as defined above. The document relates especially to Acifluorfen, the compound in which X 1  is 2-chloro, X 2  is 4-trifluoromethyl, X 3  is hydrogen and Y is COOH. 
     According to this prior art document, the product is purified by selectively dissolving unwanted isomers and other by-products in a suitable solvent. Examples of solvents which are said to be suitable for this purpose include hydrocarbons such as pentane, hexane, heptane, cyclopentane, cyclohexane, cycloheptane, benzene, toluene, xylenes and mixtures of xylenes, ethylbenzene, cumene, pseudo-cumene, ethyl-toluene and trimethylbenzene. Alternatively, it is suggested that chlorohydrocarbons may be used and examples given are 1,2-dichloroethane, methylene chloride, chloroform and chlorobenzene. Xylenes appear to be especially preferred and suggested amounts are about 0.35 to 0.45 moles of xylenes per mole of crude Acifluorfen. The crude nitration product is dissolved in the chosen solvent at elevated temperature and maintained at this temperature for a considerable period of time. On cooling, Acifluorfen crystallises out and is collected by centrifugation. The product obtained by the authors of GB-A-2103214 is said to be 82% pure. 
     However, the present inventors have found that the process described in GB-A-2103214, although partially effective, does not appear to give material of this degree of purity. In any case, it is desirable to be able to obtain material of an even greater degree of purity than specified in the prior art, particularly if additional process steps are required in order to obtain the required herbicidal compound. 
     Therefore in a first aspect of the present invention there is provided a process for the purification of a compound of general formula I:                    
     wherein: 
     R 1  is hydrogen or C 1 -C 6  alkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl (any of which may potionally be substituted with one or more substituents selected from halogen and OH) or COOH, COH, COOR 4 , COR 6 , CONR 4 R 5  or CONHSO 2 R 4 ; 
     R 4  and R 5  are each independently hydrogen or C 1 -C 4  alkyl optionally substituted with one or more halogen atoms; 
     R 6  is a halogen atom or a group R 4 ; 
     R 2  is hydrogen or halo; 
     R 3  is C 1 -C 4  alkyl, C 2 -C 4  alkenyl or C 2 -C 4  alkynyl, any of which may optionally be substituted with one or more halogen atoms, or halo; 
     or, where appropriate, a salt thereof; 
     from a mixture containing the compound of general formula I together with one or more isomers or di-nitrated analogues thereof; 
     the process comprising dissolving the mixture in a suitable crystallising solvent and recrystallising the product from the resulting crystallisation solution; 
     characterised in that the crystallisation solution contains not more than 25% loading of the compound of general formula I and in that the temperature to which the solution is cooled for crystallisation is not greater than about 30° C. 
     In the present specification, loading is defined as:          weight                 of                 pure                 compound                 of                 formula                 I   ×   100         weight                 of                 pure                 compound                 of                 formula                 I     +     weight                 of                 solvent                       
     In order to calculate the loading of the crystallisation solution, it is therefore essential to know the amount of isomer of general formula I present in the product mixture. 
     Using the process of the present invention, it is possible to obtain a product of greater than 90% purity. This is a significant advantage when the product is a herbicide as regulatory authorities usually demand an active ingredient of a very high level of purity with minimal impurities. The advantage may be even greater when the product produced is an intermediate and additional steps must be carried out as reagents are not wasted in reacting with unwanted by-products. 
     The process of the present invention differs significantly from the process described in. GB-A-2103214. The authors of that document stated that, for xylenes, the optimum amount of product loading is from 0.35 to 0.45 moles of xylene per mole of Acifluorfen. This is a solution containing at least 88% w/w of Acifluorfen whereas, in the present invention, the crystallisation solution contains not more than 25% loading of Acifluorfen. In a typical crude mixture containing about 70% Acifluorfen, this corresponds to a crystallisation solution containing about 32% w/w of the crude mixture. 
     In the context of the present invention, compounds of general formula I are designated 4′-nitro isomers. 
     Other components of the product mixture which may be present include the 2′-nitro isomer of general formula:                    
     the 6′-nitro isomer:                    
     and the dinitro isomers (1) and (2):                    
     A further unwanted by-product formed by nitration of an isomer present as an impurity in the reactant is (3):                    
     It is particularly important that purification of the desired product of general formula I should remove all, or substantially all, of the 2′-nitro isomer since this is the most difficult isomer to separate from the product by other methods. In addition, if the compound of general formula I is to be used as starting material in a further reaction, other nitrated isomers are also likely to react and this causes wastage of reagents. Again, the 2′-nitro isomer is a particularly important impurity as many of its reaction products are also difficult to separate from the reaction products of compounds of general formula I. 
     In the context of the present invention, the term “C 1 -C 6  alkyl” refers to a saturated straight or branched hydrocarbon chain containing from 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, t-butyl, n-pentyl and n-hexyl. The term “C 1 -C 4  alkyl” is a subset of C 1 -C 6  alkyl and refers to an alkyl group having up to 4 carbon atoms. 
     The term “C 2 -C 6  alkenyl” refers to a straight or branched hydrocarbon chain containing from 2 to 6 carbon atoms and having at least one double bond. Examples include ethenyl, allyl, propenyl and hexenyl. The term “C 2 -C 4  alkenyl” is a subset of C 2 -C 6  alkenyl and refers to an alkenyl group having up to 4 carbon atoms. 
     The term “C 2 -C 6  alkynyl” refers to a straight or branched hydrocarbon chain containing from 2 to 6 carbon atoms and having at least one triple bond. Examples include ethynyl, propynyl and hexynyl. The term “C 2 -C 4  alkynyl” is a subset of C 2 -C 6  alkynyl and refers to an alkynyl group having up to 4 carbon atoms. 
     The term “halogen” refers to fluorine, chlorine, bromine or iodine and the corresponding term “halo” refers to fluoro, chloro, bromo or iodo. 
     Only a narrow range of solvents is suitable for use in the present invention with examples being aromatic hydrocarbons, such as xylenes or mixtures of xylenes, and haloaromatics such as o-chlorotoluene, p-chlorotoluene, benzotrifluoride, 3,4-dichlorobenzotrifluoride, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, fluorobenzene, bromobenzene, and 2-fluorotoluene. Mixtures of any of the above solvents may also be suitable and also mixtures containing aromatic hydrocarbons with a co-solvent which may be one of the solvents mentioned above but may, alternatively be chosen from a much wider range of solvents including aliphatic hydrocarbons, esters, ethers, nitriles and halohydrocarbons. 
     Xylenes have been found to be particularly suitable solvents for use in the present invention with o-xylene giving better results than other xylenes or mixtures of xylenes. 
     The optimum loading of the crystallisation varies considerably according to the solvent which is chosen but is, in any case, not greater than about 25%. More typically, optimum loading is from 8% to 20%. For many solvents, for example xylenes, the loading may be, for example, from about 15 to 20% but with a few solvents it is necessary to reduce the loading even further with a product mixture loading of about 8 to 10% being used. 
     Although the temperature to which the solution is cooled to effect crystallisation may be as high as 30° C., the purity of the product may be increased considerably by reducing the temperature somewhat. It is greatly preferred, therefore that the temperature to which the solution is cooled to achieve crystallisation is not above 20° C., with about 5° to 15° C. being an optimal range. This is in contrast to the process described in GB-A-2103214 in which the crystallisation temperature recommended for optimum results is about 25° C. 
     A further factor which has been found to affect the purity of the product is the length of time for which the mixture is allowed to stand after crystallisation before recovery of the product. It has been found that many 2′-nitro isomers of general formula I are metastable in solution and tend to crystallise slowly, contaminating the desired product and reducing its purity after crystallisation. Therefore, it is preferred that the product slurry, after achieving crystallisation temperature, is not held for more than about four hours, more usually from about 1 to 2 hours, before physical separation of the product from the mother liquors. 
     Crystallisation may be achieved by any suitable method such as seeding the crystallisation solution with crystals of a pure compound of general formula I. It may be advantageous to carry out the seeding in several stages starting when the crystallisation solution is still hot and adding further crystals as it cools. In some circumstances, seeding of the crystallisation solution may not be necessary and cooling of the solution will cause crystallisation of the product. 
     The product may be separated from the slurry after crystallisation by any appropriate method but filtration is very often the most convenient way of doing this. 
     The mixture to be purified may be the crude product of a process for the nitration of a compound of general formula II:                    
     wherein R 1 , R 2  and R 3  are as defined for general formula I. 
     Any conventional nitration method may be used, for example the nitration method disclosed in GB-A-2103214. 
     In one suitable method, the nitration agent may be nitric acid or a mixture of nitric and sulphuric acids although other types of nitrating agent may also be used. The reaction may take place in an organic solvent and suitable solvents include halogenated solvents such as dichloromethane (DCM), ethylene dichloride (EDC), chloroform, tetrachloroethylene (perklone) and dichlorobenzotrifluoride (DCBTF). Alternatively, solvents such as acetic acid, acetic anhydride, acetonitrile, ethers such as tetrahydrofuran (THF) or dioxane, sulpholane, nitrobenzene, nitromethane, liquid sulphur dioxide or liquid carbon dioxide. It is also advantageous to conduct the reaction in the presence of acetic anhydride and, in this case, it is preferred that the molar ratio of acetic anhydride to compound of general formula II is from about 1:1 to 3:1. The reaction temperature may be from about −15° to 15° C., more usually from about −10° to 10° C. 
     After the nitration reaction, the crude product must be removed from the reaction solvent and taken up in the crystallisation solvent. This may be achieved by washing with water to remove any acetic anhydride, acetic acid or mineral acid and then stripping off the reaction solvent completely, melting the product mixture and then taking up the melt in the crystallisation solvent. Alternatively, the product can be extracted from the nitration solvent as a salt (for example the sodium salt) into water and the solvent separated off for recycling. The salt solution may then be acidified in the presence of the hot recrystallisation solvent in order to extract the product for recrystallisation. 
     When the nitration process is combined with either of these work-ups and the recrystallisation process of the first aspect of the invention, it is possible to obtain a product of over 90% purity in a yield of greater than 70%. 
     The step of taking up the crude product in the crystallisation solvent may be preceded by an initial partial purification step which itself forms a further aspect of the present invention. 
     In this aspect of the invention, there is provided a process for partial purification of a product mixture obtained from the nitration of a compound of general formula II to give a compound of general formula I, the process comprising removing the reaction solvent and treating the resultant crude product with a mixture of water and a water-miscible polar solvent. 
     In one method of achieving partial purification, any acetic anhydride may be hydrolysed with water to give acetic acid and this, or acetic acid from any other source, may be left in the reaction mass to act as the polar solvent. The reaction solvent may then be removed by distillation or steam distillation leaving a molten crude product containing some acetic acid which may then be treated with additional quantities of acetic acid and water to facilitate partial purification without substantial dissolution of the required isomer. 
     Alternatively, the crude product of the nitration reaction, after washing and removal of the reaction solvent, may be treated with a mixture of a polar solvent and water to achieve partial dissolution of impurities and isomers without substantial loss of the desired product which can then be recovered by filtration. In this case, suitable polar solvents include solvents such as formic acid, acetic acid, propionic acid, methanol, acetonitrile and acetone. 
     The proportion of polar solvent to water may be in the range of from about 3:7 to 7:3, more particularly from about 2:3 to 3:2, and the amount of crude nitrated isomer mixture in the polar solvent/water solution may be from about 10 to 80% by weight, preferably about 15 to 30% by weight. The initial purification step may be carried out at a temperature of from about 10° to 60° C., more usually from about 15° to 30° C. 
     An initial purification process such as those described above leads to an improvement in the quality of the crude nitration product from about 70% strength (i.e. 70% by weight of the desired isomer of general formula I) to about 80% strength. A nitration process followed by the initial purification step and the recrystallisation process of the first aspect of the invention is high yielding with a recovery of the desired isomer of greater than 90% and often greater than 95%. The initial purification step of the second aspect of the invention is particularly effective for the removal of products of over nitration and also other impurities which commonly occur in a product derived from a multi-step synthesis. The product from the initial purification process has improved characteristics for purification by recrystallisation. 
     Although the process of the invention may be used for the purification of any compound of general formula I, it is especially preferred that R 2  is chloro and R 3  is trifluoromethyl. Particularly preferred compounds of general formula I are those in which R 1  is COOH or CONHSO 2 CH 3 . These compounds are 5-(2-chloro-α,α,α-trifluoro-4-tolyloxy)-2′-nitrobenzoic acid (Acifluorfen) and 5-(2-chloro-α,α,α-trifluoro-4-tolyloxy)-N-methanesulphonyl-2′-nitro-benzamide (Fomesafen), both of which are potent herbicidal compounds. 
     In addition to being a herbicide in its own right, Acifluorfen may also serve as an intermediate in the synthesis of Fomesafen. The Acifluorfen may be converted to the acid chloride which may then be reacted with methane sulphonamide to give Fomesafen. Both of these steps may be carried out by conventional methods, for example as set out in EP-A-0003416. It is a particular advantage when using this method to start out with pure Acifluorfen as the reaction with methane sulphonamide is an expensive process and it is highly desirable not to waste reagents by sulphonamidating unwanted nitro-isomers to produce unwanted isomers of Fomesafen. 
     The present invention therefore provides a route for the synthesis of pure Acifluorfen and its subsequent conversion to pure Fomesafen. 
    
    
     The invention will now be further illustrated with reference to the following examples. 
     EXAMPLE 1 
     General Procedure for Recrystallisation of Solid Acifluorfen 
     Solid crude Acifluorfen was added to the recrystallisation solvent and heated to about 80° C. to dissolve. Any water was separated off and remaining traces of water were removed by azeotropic distillation. The solution was cooled to about 60° C. and a seed of pure Acifluorfen was added and further seeds added at 5° C. intervals as the solution was cooled until crystallisation occurred. Cooling was continued to the required temperature and the product was isolated by filtration and washed with a little fresh solvent. 
     The crude Acifluorfen had the following composition: 
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 Acifluorfen 
                 69-75% 
               
               
                   
                 2′-nitro 
                 7-9% 
               
               
                   
                 6′-nitro 
                 3.5-4.5% 
               
               
                   
                 Isomer (3) 
                 4.5-5%   
               
               
                   
                 Dinitros 
                 0.5-2%   
               
               
                   
                   
               
            
           
         
       
     
     EXAMPLE 2 
     General Procedure for Extraction of Acifluorfen from its Sodium Salt and Recrystallisation 
     Acifluorfen sodium salt solution at 10-40% concentration (as free acid) was mixed with the recrystallisation solvent and heated to 80° C. Mineral acid was added to adjust the pH of the solution to 3-3.5 and the two layers were allowed to separate. The aqueous layer was separated and the organic layer was washed with one third volume water at 70-80° C. The aqueous layer was removed and the solution dried by azeotropic removal of water. The solution was cooled to effect crystallisation and the product recovered by filtration. 
     Tables I and II give the results for the purification procedure described in Example 1 and Tables III and IV give results for the purification process described in Example 2. In each case, a variety of different solvents, loadings of the crystallisation solution, filtration temperatures and stir times were used. In Tables I to IV, the following abbreviations are used: 
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 Exp 
                 Experiment No.; 
               
               
                   
                 Stg. Mtl. Str. 
                 Starting material strength (i.e. % required 
               
               
                   
                   
                 product in mixture); 
               
               
                   
                 Wt Solv. g 
                 Weight of crystallisation solvent in grams; 
               
               
                   
                 TEA 
                 triethylamine; 
               
               
                   
                 AcOH 
                 acetic acid; 
               
               
                   
                 MCB 
                 monochlorobenzene; 
               
               
                   
                 MDCB 
                 m-dichlorobenzene; 
               
               
                   
                 ODCB 
                 o-dichlorobenzene 
               
               
                   
                 tech xylene 
                 mixture of xylenes; 
               
               
                   
                 Tol 
                 toluene; 
               
               
                   
                 cyclohex 
                 cyclohexane. 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                   
                 TABLE I 
               
             
            
               
                   
                   
               
               
                   
                 Stg. 
                   
                   
                   
                   
                   
                   
               
               
                   
                 Mtl. 
                   
                   
                 Filt. 
                   
                   
                 Product Analysis % w/w 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Str 
                   
                 Loading 
                 Temp. 
                 Stir 
                 Recovery 
                 Total 
                 Isomer (3) 
                 Product 
                 2′-nitro 
                 6′-nitro 
               
               
                 Exp. 
                 % 
                 Solvent 
                 % 
                 ° C. 
                 Time hr 
                 % 
                 dinitro 
                 % 
                 % 
                 % 
                 % 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                  1 
                 71.7 
                 2-Chlorotoluene 
                 14.99 
                 30 
                 0.00 
                 59.33 
                 0.8 
                 0.8 
                 95.6 
                 0 
                 0 
               
               
                  2 
                 71.7 
                 2-Chlorotoluene 
                 20.00 
                 30 
                 0.00 
                 62.98 
                 0.5 
                 0.6 
                 91.3 
                 3.7 
                 0.1 
               
               
                  3 
                 71.7 
                 2-Chlorotoluene 
                 19.05 
                 30 
                 0.00 
                 69.89 
                 0.8 
                 0.6 
                 90.2 
                 5.9 
                 0 
               
               
                  4 
                 72.2 
                 2-Chlorotoluene 
                 15.00 
                 30 
                 0.00 
                 60.05 
                 0.7 
                 1 
                 93.8 
                 0.6 
                 0 
               
               
                  5 
                 72.2 
                 2-Chlorotoluene 
                 15.00 
                 30 
                 0.00 
                 47.23 
                 0.5 
                 1.2 
                 90.8 
                 1 
                 0 
               
               
                  6 
                 72.2 
                 2-Chlorotoluene 
                 20.11 
                 30 
                 0.00 
                 65.33 
                 0.7 
                 1 
                 78.8 
                 8.2 
                 0 
               
               
                  7 
                 75.4 
                 2-Chlorotoluene 
                 6.48 
                 15 
                 0.50 
                 54.83 
                 0.52 
                 0.5 
                 93.9 
                 0.4 
                 0 
               
               
                  8 
                 79.7 
                 2-Chlorotoluene 
                 11.59 
                 15 
                 0.50 
                 74.08 
                 0.5 
                 0.3 
                 91.6 
                 6.3 
                 0.1 
               
               
                  9 
                 85.5 
                 2-Chlorotoluene 
                 15.00 
                 30 
                 0.00 
                 74.83 
                 0.2 
                 0.2 
                 90.7 
                 7.8 
                 0 
               
               
                 10 
                 69.3 
                 2-Chlorotoluene/TEA 
                 19.86 
                 30 
                 0.00 
                 52.97 
                 0.6 
                 0.5 
                 93.9 
                 0.9 
                 0 
               
               
                 11 
                 71.2 
                 2-Fluorotoluene 
                 15.04 
                 15 
                 1 
                 63.63 
                 0.5 
                 0.8 
                 81.6 
                 5.2 
                 0.1 
               
               
                 12 
                 77.16 
                 4-Chlorotoluene 
                 9.98 
                 15 
                 1.00 
                 76.21 
                 0.2 
                 0.25 
                 92 
                 7.5 
                 0 
               
               
                 13 
                 67.9 
                 AcOH/water 40/60 
                 21.50 
                 55 
                 1.00 
                 96.59 
                 1.73 
                 6.2 
                 72 
                 10 
                 5 
               
               
                 14 
                 67.9 
                 AcOH/water 40/60 
                 21.50 
                 45 
                 1.00 
                 90.34 
                 1.1 
                 6.2 
                 72.2 
                 10.2 
                 4.6 
               
               
                 15 
                 70.3 
                 AcOH/water 40/60 
                 21.61 
                 55 
                 1.00 
                 90.13 
                 1.98 
                 4.2 
                 71.1 
                 8.7 
                 4.3 
               
               
                 16 
                 69.6 
                 AcOH/water 42/58 
                 16.65 
                 20 
                 16.00 
                 85.67 
                 1.3 
                 3.3 
                 75.4 
                 8.9 
                 4.4 
               
               
                 17 
                 70.3 
                 AcOH/water 42/58 
                 21.60 
                 55/45 
                 1.00 
                 92.33 
                 1.45 
                 3.7 
                 73.3 
                 9 
                 4.2 
               
               
                 18 
                 70.3 
                 AcOH/water 42/58 
                 21.61 
                 55 
                 1.00 
                 91.46 
                 1.5 
                 3.5 
                 74.3 
                 9.1 
                 3.7 
               
               
                 19 
                 69.5 
                 AcOH/water 45/55 
                 16.09 
                 20 
                 16.00 
                 87.25 
                 0.9 
                 2 
                 79.7 
                 10.1 
                 4.5 
               
               
                 20 
                 69.5 
                 AcOH/water 45/55 
                 19.77 
                 20 
                 16.00 
                 85.82 
                 1.2 
                 2.2 
                 76.5 
                 10.1 
                 4.7 
               
               
                 21 
                 71.7 
                 AcOH/water 45/55 
                 19.48 
                 20 
                 0.50 
                 74.72 
                 0.5 
                 1.4 
                 80.7 
                 9.8 
                 0.8 
               
               
                 22 
                 68.9 
                 AcOH/water 50/50 
                 40.68 
                 22 
                 2 
                 96.41 
                 0.43 
                 2.25 
                 79.2 
                 10 
                 4.4 
               
               
                 23 
                 68.9 
                 AcOH/water 50/50 
                 31.58 
                 22 
                 2 
                 86.22 
                 0.38 
                 2.25 
                 78.8 
                 10.2 
                 4.45 
               
               
                 24 
                 75.4 
                 Benzotrifluoride 
                 5.88 
                 15 
                 0.50 
                 67.41 
                 0.6 
                 0.6 
                 90.8 
                 1.8 
                 0 
               
               
                 25 
                 75.4 
                 Benzotrifluoride 
                 7.61 
                 15 
                 0.50 
                 69.16 
                 0.62 
                 0.67 
                 88 
                 6.04 
                 0 
               
               
                 26 
                 75.4 
                 Benzotrifluoride 
                 7.61 
                 10 
                 0.50 
                 80.17 
                 0.67 
                 0.62 
                 88.8 
                 6.6 
                 0 
               
               
                 27 
                 75.5 
                 Benzotrifluoride 
                 5.92 
                 15 
                 1.00 
                 77.06 
                 0.6 
                 0.9 
                 91.1 
                 6.2 
                 0.2 
               
               
                 28 
                 75.5 
                 Benzotrifluoride 
                 5.92 
                 10 
                 0.50 
                 79.82 
                 0.66 
                 0.7 
                 90.4 
                 6.74 
                 0.18 
               
               
                 29 
                 75.5 
                 Benzotrifluoride 
                 7.63 
                 15 
                 0.50 
                 79.72 
                 0.68 
                 0.7 
                 90.4 
                 8.1 
                 0.13 
               
               
                 30 
                 76.5 
                 Benzotrifluoride 
                 10.59 
                 15 
                 0.50 
                 80.08 
                 0.6 
                 0.4 
                 88.4 
                 9.1 
                 0 
               
               
                 31 
                 71.2 
                 Bromobenzene 
                 15.04 
                 15 
                 1 
                 70.51 
                 0.5 
                 1.1 
                 85.5 
                 5.9 
                 0.15 
               
               
                 32 
                 75.4 
                 MCB 
                 6.34 
                 15 
                 0.50 
                 40.04 
                 0.54 
                 0.7 
                 94.3 
                 0 
                 0 
               
               
                 33 
                 75.5 
                 MCB 
                 8.21 
                 15 
                 0.50 
                 52.09 
                 0.5 
                 0.8 
                 96.7 
                 0 
                 0 
               
               
                 34 
                 75.5 
                 MCB 
                 8.21 
                 10 
                 0.50 
                 57.02 
                 0.49 
                 0.75 
                 95.9 
                 0.2 
                 0 
               
               
                 35 
                 77.16 
                 MCB 
                 14.97 
                 15 
                 1 
                 79.35 
                 0.14 
                 0.25 
                 86.7 
                 8.8 
                 0 
               
               
                 36 
                 77.16 
                 MCB 
                 13.02 
                 15 
                 1 
                 79.00 
                 0.2 
                 0.2 
                 87.6 
                 8.9 
                 0 
               
               
                 37 
                 79.7 
                 MCB 
                 11.41 
                 15 
                 0.50 
                 67.90 
                 0.49 
                 0.5 
                 96.2 
                 3.4 
                 0 
               
               
                 38 
                 79.9 
                 MCB 
                 11.99 
                 15 
                 1 
                 78.11 
                 1.57 
                 0.3 
                 92.5 
                 1.66 
                 0.1 
               
               
                 39 
                 79.9 
                 MCB 
                 14.98 
                 15 
                 1 
                 81.01 
                 1.7 
                 0.4 
                 90.5 
                 4.4 
                 0.1 
               
               
                 40 
                 79.9 
                 MCB 
                 14.98 
                 15 
                 1 
                 83.40 
                 1.6 
                 0.5 
                 91.2 
                 4.7 
               
               
                 41 
                 71.2 
                 MDCB 
                 15.04 
                 15 
                   
                 77.39 
                 0.6 
                 0.8 
                 86.5 
                 7 
                 0.2 
               
               
                 42 
                 71.2 
                 MDCB 
                 13.01 
                   
                   
                 0.00 
                 0.6 
                 0.8 
                 84.5 
                 7.4 
                 0.2 
               
               
                 43 
                 68.9 
                 o-xylene 
                 11.97 
                 15 
                 3.00 
                 54.15 
                 0.38 
                 1.1 
                 88 
                 0.63 
                 0.1 
               
               
                 44 
                 68.9 
                 o-xylene 
                 9.90 
                 15 
                 3.00 
                 53.31 
                 0.39 
                 1 
                 87.4 
                 0.8 
                 0.11 
               
               
                 45 
                 68.9 
                 o-xylene 
                 13.75 
                 15 
                 1.00 
                 59.26 
                 0.34 
                 0.8 
                 85.2 
                 2.85 
                 0.2 
               
               
                 46 
                 69 
                 o-xylene 
                 17.97 
                 25 
                 1 
                 70.87 
                 4.2 
                 1 
                 91.4 
                 1.1 
                 0.8 
               
               
                 47 
                 71.2 
                 o-xylene 
                 16.51 
                 15 
                 1.00 
                 61.20 
                 9.5 
                 0.9 
                 90.5 
                 0.6 
                 0.1 
               
               
                 48 
                 71.2 
                 o-xylene 
                 13.01 
                 15 
                 1.00 
                 78.13 
                 0.85 
                 0.84 
                 84.5. 
                 7.4 
                 0.2 
               
               
                 49 
                 71.4 
                 o-xylene 
                 16.10 
                 15 
                 1.00 
                 62.24 
                 0.3 
                 0.7 
                 91.9 
                 0 
                 0 
               
               
                 50 
                 73.3 
                 o-xylene 
                 10.02 
                 15 
                 1.00 
                 61.26 
                 0.59 
                 0.8 
                 94.9 
                 1.06 
                 0.2 
               
               
                 51 
                 73.3 
                 o-xylene 
                 15.02 
                 15 
                 1.00 
                 71.23 
                 0.74 
                 0.63 
                 87.8 
                 7.3 
                 0.2 
               
               
                 52 
                 77.16 
                 o-xylene 
                 11.98 
                 30 
                 1 
                 63.43 
                 0.16 
                 0.3 
                 91.3 
                 5.1 
                 0.04 
               
               
                 53 
                 77.16 
                 o-xylene 
                 9.98 
                 20 
                 1 
                 73.03 
                 0.15 
                 0.25 
                 93.6 
                 5.9 
                 0 
               
               
                 54 
                 79.9 
                 o-xylene 
                 11.99 
                 15 
                 1 
                 78.18 
                 1.7 
                 0.4 
                 96 
                 0.8 
                 0.1 
               
               
                 55 
                 79.9 
                 o-xylene 
                 11.99 
                 25 
                 1 
                 77.43 
                 1.76 
                 0.2 
                 93.4 
                 2.2 
                 0.1 
               
               
                 56 
                 79.9 
                 o-xylene 
                 14.98 
                 25 
                 1 
                 79.84 
                 1.2 
                 0.3 
                 91.3 
                 3.8 
                 0.1 
               
               
                 57 
                 67.9 
                 ODCB 
                 9.82 
                 15 
                 1.00 
                 62.78 
                 0.54 
                 2.3 
                 93.1 
                 0 
                 0 
               
               
                 58 
                 67.9 
                 ODCB 
                 15.00 
                 15 
                 1.00 
                 68.43 
                 0.66 
                 1.5 
                 86.6 
                 5.5 
                 0 
               
               
                 59 
                 68.9 
                 ODCB 
                 9.90 
                 15 
                 1.00 
                 67.00 
                 0.35 
                 1.1 
                 90 
                 0.35 
                 0.1 
               
               
                 60 
                 68.9 
                 ODCB 
                 11.97 
                 15 
                 1.00 
                 69.84 
                 0.39 
                 1.05 
                 90.1 
                 0.63 
                 0.1 
               
               
                 61 
                 68.9 
                 ODCB 
                 9.90 
                 15 
                 1.00 
                 64.40 
                 0.41 
                 1.3 
                 89 
                 0.66 
                 0.2 
               
               
                 62 
                 68.9 
                 ODCB 
                 9.90 
                 15 
                 3.00 
                 66.24 
                 0.4 
                 1.05 
                 90.2 
                 1.4 
                 0.1 
               
               
                 63 
                 68.9 
                 ODCB 
                 11.96 
                 15 
                 1.00 
                 69.42 
                 0.3 
                 1.2 
                 89.3 
                 2.2 
                 0.3 
               
               
                 64 
                 68.9 
                 ODCB 
                 11.97 
                 15 
                 3.00 
                 70.51 
                 0.26 
                 1 
                 88 
                 3.6 
                 0.2 
               
               
                 65 
                 68.9 
                 ODCB 
                 13.80 
                 15 
                 1.00 
                 70.13 
                 0.25 
                 0.8 
                 84.8 
                 5 
                 0.2 
               
               
                 66 
                 69 
                 ODCB 
                 17.97 
                 15 
                 1 
                 78.00 
                 3.7 
                 0.9 
                 89.7 
                 0.5 
                 0 
               
               
                 67 
                 69.6 
                 ODCB 
                 9.81 
                 15 
                 0.50 
                 42.94 
                 0.72 
                 0.94 
                 92.8 
                 0.1 
                 0 
               
               
                 68 
                 69.93 
                 ODCB 
                 20.45 
                 30 
                   
                 78.43 
                 0.4 
                 0.6 
                 88.4 
                 7.7 
                 0 
               
               
                 69 
                 70 
                 ODCB 
                 14.86 
                 15 
                 1.00 
                 58.16 
                 0.77 
                 0.9 
                 95.9 
                 0.2 
                 0 
               
               
                 70 
                 70 
                 ODCB 
                 19.85 
                 15 
                 1.00 
                 76.20 
                 0.61 
                 1.1 
                 88.8 
                 7.3 
                 0.3 
               
               
                 71 
                 72 
                 ODCB 
                 9.90 
                 15 
                 1.00 
                 67.09 
                 0.56 
                 1.7 
                 94.2 
                 0.6 
                 0.14 
               
               
                 72 
                 73.3 
                 ODCB 
                 9.83 
                 15 
                 1.00 
                 68.58 
                 0.81 
                 0.6 
                 93.2 
                 0.3 
                 0.1 
               
               
                 73 
                 73.3 
                 ODCB 
                 11.99 
                 15 
                 1.00 
                 69.44 
                 0.71 
                 0.8 
                 92.8 
                 0.5 
                 0.1 
               
               
                 74 
                 73.3 
                 ODCB 
                 13.80 
                 15 
                 1.00 
                 73.58 
                 1.1 
                 0.6 
                 92.2 
                 3.13 
                 0.16 
               
               
                 75 
                 75.5 
                 ODCB 
                 9.81 
                 15 
                 0.50 
                 66.15 
                 0.59 
                 1 
                 94.4 
                 3.4 
                 0 
               
               
                 76 
                 75.5 
                 ODCB 
                 12.04 
                 15 
                 1.00 
                 73.69 
                 0.57 
                 1.06 
                 89.3 
                 6.2 
                 0 
               
               
                 77 
                 76.5 
                 ODCB 
                 9.90 
                 15 
                 0.50 
                 75.90 
                 0.5 
                 0.5 
                 97.7 
                 0.9 
                 0 
               
               
                 78 
                 77.16 
                 ODCB 
                 7.96 
                 15 
                 1 
                 69.83 
                 0.2 
                 0.4 
                 95.2 
                 0.1 
                 0 
               
               
                 79 
                 77.16 
                 ODCB 
                 8.97 
                 15 
                 1 
                 78.49 
                 0.2 
                 0.3 
                 96.3 
                 1.7 
                 0 
               
               
                 80 
                 77.16 
                 ODCB 
                 14.97 
                 25 
                 1 
                 81.37 
                 0.2 
                 0.45 
                 90.9 
                 5.4 
                 0 
               
               
                 81 
                 77.16 
                 ODCB 
                 9.98 
                 15 
                 1 
                 81.30 
                 0.15 
                 0.4 
                 92.2 
                 6.8 
                 0 
               
               
                 82 
                 79.7 
                 ODCB 
                 9.91 
                 15 
                 1.00 
                 75.75 
                 0.5 
                 0.4 
                 97.5 
                 0 
                 0 
               
               
                 83 
                 80.7 
                 ODCB 
                 9.91 
                 15 
                 0.50 
                 80.05 
                 0.1 
                 0.4 
                 96.9 
                 0.5 
                 0 
               
               
                 84 
                 80.7 
                 ODCB 
                 12.47 
                 15 
                 0.50 
                 86.39 
                 0 
                 0.3 
                 90.7 
                 7.2 
                 0 
               
               
                 85 
                 69.3 
                 ODCB/TEA 
                 19.86 
                 30 
                 0.00 
                 64.76 
                 0.2 
                 0.7 
                 75.5 
                 2.6 
                 0 
               
               
                 86 
                 79.9 
                 p-xylene 
                 11.02 
                 25 
                 1 
                 77.35 
                 2.06 
                 0.2 
                 93.9 
                 1.63 
                 0.1 
               
               
                 87 
                 79.9 
                 p-xylene 
                 14.00 
                 25 
                 1 
                 77.21 
                 1.88 
                 0.3 
                 91.8 
                 3.4 
                 0.1 
               
               
                 88 
                 79.9 
                 p-xylene 
                 11.02 
                 15 
                 1 
                 81.04 
                 2 
                 0.4 
                 90.6 
                 3.6 
                 0 
               
               
                 89 
                 69.3 
                 Perklone/TEA 
                 14.77 
                 30 
                 0.00 
                 60.59 
                 0 
                 3.3 
                 72.4 
                 8.3 
                 0 
               
               
                 90 
                 70 
                 tech xylene 
                 9.90 
                 15 
                 1.00 
                 53.10 
                 0.85 
                 1 
                 96.1 
                 0.75 
                 0.1 
               
               
                 91 
                 70 
                 tech xylene 
                 15.86 
                 15 
                 1.00 
                 74.67 
                 0 
                 0.8 
                 88.3 
                 9.4 
                 0.3 
               
               
                 92 
                 77.16 
                 tech xylene 
                 9.98 
                 30 
                 1 
                 67.69 
                 0.15 
                 0.2 
                 86.6 
                 9.5 
                 0 
               
               
                 93 
                 77.16 
                 tech xylene 
                 11.98 
                 30 
                 1 
                 80.59 
                 0.2 
                 0.3 
                 88.7 
                 9.9 
                 0.1 
               
               
                 94 
                 79.2 
                 tech xylene 
                 12.04 
                 20 
                 1 
                 75.79 
                 0.14 
                 0.4 
                 84.8 
                 10.3 
                 0.16 
               
               
                 95 
                 79.2 
                 tech xylene 
                 12.04 
                 30 
                 1 
                 44.83 
                 0.14 
                 0.3 
                 85A 
                 10.7 
                 0.17 
               
               
                 96 
                 69.93 
                 tech-xylene 
                 16.86 
                 25 
                 0.00 
                 53.70 
                 0.4 
                 0.6 
                 88.9 
                 6.2 
                 0 
               
               
                 97 
                 69.3 
                 Tol/cyclohex/TEA 
                 20.00 
                 30 
                 0.00 
                 43.06 
                 1 
                 0.5 
                 82.8 
                 6.7 
                 0 
               
               
                 98 
                 69.93 
                 Toluene 
                 20.48 
                 30 
                 0.00 
                 50.58 
                 0.8 
                 0.7 
                 88.3 
                 5.7 
                 0 
               
               
                 99 
                 71.7 
                 Toluene 
                 20.00 
                 25 
                 1.00 
                 43.06 
                 0.5 
                 0.5 
                 88.8 
                 8.5 
                 0 
               
               
                 100  
                 76.5 
                 Toluene 
                 13.88 
                 15 
                 0.50 
                 75.20 
                 0.5 
                 0.3 
                 90 
                 8.5 
                 0 
               
               
                 101  
                 71.7 
                 Toluene/cyclohex 
                 20.00 
                 25 
                 1.00 
                 59.12 
                 0.6 
                 0.6 
                 87.6 
                 9.4 
                 0 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                   
                 TABLE II 
               
             
            
               
                   
                   
               
               
                   
                 Stg. 
                   
                   
                   
                   
                   
                   
               
               
                   
                 Mtl. 
                   
                   
                 Filt. 
                 Stir 
                   
                 Product Analysis 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Str 
                   
                 Loading 
                 Temp. 
                 Time 
                 Recovery 
                 Total di- 
                 Isomer (3) 
                 Product 
                 2′-nitro 
                 6′-nitro 
               
               
                 Exp. 
                 % 
                 Solvent 
                 % 
                 ° C. 
                 (hr) 
                 % 
                 dinitro 
                 nitros (%) 
                 (%) 
                 (%) 
                 (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 102 
                 66.2 
                 2-Chlorotoluene 
                 8.9 
                 15 
                   
                 60.2 
                 0 
                 0.9 
                 57 
                 0.61 
                 0.4 
               
               
                 103 
                 71.8 
                 4-Chlorotoluene 
                 10 
                   
                   
                 61.8 
                 0 
                 0.85 
                 93.9 
                 0 
                 0 
               
               
                 104 
                 71.8 
                 4-Chlorotoluene 
                 6.15 
                   
                   
                 52.9 
                 0.22 
                 1.2 
                 93.8 
                 0.5 
                 0.23 
               
               
                 105 
                 71.8 
                 4-Chlorotoluene 
                 8.19 
                   
                   
                 60 
                 0 
                 1.2 
                 93.7 
                 0.5 
                 0.23 
               
               
                 106 
                 66.2 
                 4-Chlorotoluene 
                 11.7 
                 30 
                   
                 36.2 
                 0 
                 0.9 
                 89.1 
                 0.57 
                 0.25 
               
               
                 107 
                 71.8 
                 4-Chlorotoluene 
                 10.23 
                   
                   
                 66.3 
                 0 
                 1.1 
                 94.35 
                 0.6 
                 0.3 
               
               
                 108 
                 66.2 
                 4-Chlorotoluene 
                 8.9 
                 15 
                   
                 52.9 
                 0 
                 0.9 
                 57.57 
                 0.65 
                 0.4 
               
               
                 109 
                 71.8 
                 4-Chlorotoluene 
                 8 
                   
                   
                 64.7 
                 0 
                 1.1 
                 93.4 
                 0.7 
                 0.3 
               
               
                 110 
                 71 
                 4-Chlorotoluene 
                 8.9 
                 10 
                   
                 62.8 
                 0 
                 1.43 
                 90.49 
                 0.73 
                 0.53 
               
               
                 111 
                 71.8 
                 4-Chlorotoluene 
                 12.27 
                   
                   
                 70.2 
                 0 
                 1.2 
                 90 
                 3.8 
                 0.44 
               
               
                 112 
                 71.8 
                 4-Chlorotoluene 
                 12 
                   
                   
                 71.3 
                 0 
                 1 
                 90.28 
                 3.9 
                 0.35 
               
               
                 113 
                 71.8 
                 4-Chlorotoluene 
                 10 
                   
                   
                 75.4 
                 0 
                 0.7 
                 90.3 
                 4.6 
                 0.4 
               
               
                 114 
                 71.8 
                 4-Chlorotoluene 
                 14.31 
                   
                   
                 75.5 
                 0 
                 1.3 
                 88.2 
                 5.7 
                 0.56 
               
               
                 115 
                 71.8 
                 4-Chlorotoluene 
                 14 
                   
                   
                 73.6 
                 0 
                 0.9 
                 88.1 
                 6.5 
                 0.25 
               
               
                 116 
                 71.8 
                 4-Chlorotoluene 
                 16.34 
                   
                   
                 77.7 
                 0 
                 1.3 
                 87.24 
                 6.75 
                 0.58 
               
               
                 117 
                 71.8 
                 4-Chlorotoluene 
                 12 
                   
                   
                 74.9 
                 0 
                 0.9 
                 87.45 
                 7.2 
                 0.4 
               
               
                 118 
                 71.8 
                 4-Chlorotoluene 
                 16 
                   
                   
                 77.2 
                 0 
                 1 
                 86.6 
                 7.8 
                 0.4 
               
               
                 119 
                 71.8 
                 4-Chlorotoluene 
                 18 
                   
                   
                 79.6 
                 0 
                 1.35 
                 85.9 
                 8.2 
                 0.8 
               
               
                 120 
                 66.2 
                 Benzotrifluoride 
                 11.7 
                 30 
                   
                 69.1 
                 0 
                 1.5 
                 82.3 
                 5.3 
                 1.05 
               
               
                 121 
                 66.2 
                 Benzotrifluoride 
                 8.9 
                 15 
                   
                 71.1 
                 0 
                 1.05 
                 82.54 
                 6.47 
                 0.4 
               
               
                 122 
                 66.2 
                 Fluorobenzene 
                 11.7 
                 21 
                   
                 31.2 
                 0 
                 1.42 
                 87.17 
                 1.05 
                 0.52 
               
               
                 123 
                 66.2 
                 MCB 
                 8.9 
                 15 
                   
                 28.4 
                 0 
                 1.4 
                 88.7 
                 0.8 
                 0.38 
               
               
                 124 
                 66.2 
                 MCB 
                 11.7 
                 30 
                   
                 30.3 
                 0 
                 1.21 
                 86.56 
                 0.91 
                 0.52 
               
               
                 125 
                 71 
                 MCB 
                 8.9 
                  0 
                   
                 61.3 
                 0 
                 1.66 
                 89.8 
                 1.17 
                 0.7 
               
               
                 126 
                 ? 
                 o-xylene 
                 16 
                 15 
                 1 
                 57.5 
                 0.3 
                 0.9 
                 93.5 
                 0.6 
                 0.3 
               
               
                 127 
                 ? 
                 o-xylene 
                 18 
                 15 
                 1 
                 74 
                 0.3 
                 1.4 
                 87.9 
                 4.1 
                 0.4 
               
               
                 128 
                 66.2 
                 ODCB 
                 8.9 
                 15 
                   
                 51.5 
                 0 
                 0.9 
                 55.9 
                 0.6 
                 0.3 
               
               
                 129 
                 66.2 
                 Toluene 
                 8.9 
                 15 
                 2 
                 38.1 
                 0 
                 1.3 
                 85.6 
                 1.4 
                 0.7 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                   
                 TABLE III 
               
             
            
               
                   
                   
               
               
                   
                   
                   
                 Filt. 
                   
                   
                   
                 Product Analysis % w/w 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                 Loading 
                 Temp. 
                 Stir time 
                 Recovery 
                   
                 Isomer (3) 
                 Product 
                 2′-nitro 
                 6′-nitro 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Exp. 
                 Solvent 
                 Target % 
                 Act % 
                 ° C. 
                 (hr) 
                 % 
                 loss (%) 
                 (%) 
                 (%) 
                 (%) 
                 (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 130 
                 o-xylene 
                 16.00 
                 16.35 
                 15 
                 1 
                 19.16 
                 72.79 
                 0.9 
                 94.7 
                 0 
                 0 
               
               
                 131 
                 o-xylene 
                 20.06 
                 20.56 
                 15 
                 2 
                 37.22 
                 52.20 
                 0.8 
                 96.1 
                 0.2 
                 0 
               
               
                 132 
                 o-xylene 
                 16.00 
                   
                 15 
                 1 
                 39.55 
                 48.04 
                 0.8 
                 94.15 
                 0 
                 0 
               
               
                 133 
                 o-xylene 
                 20.00 
                 20.71 
                 15 
                 2 
                 45.81 
                 42.47 
                 0.9 
                 98 
                 0 
                 0 
               
               
                 134 
                 o-xylene 
                 16.00 
                   
                 15 
                 1 
                 48.97 
                 43.01 
                 0.8 
                 96.65 
                 0 
                 0 
               
               
                 135 
                 o-xylene 
                 20.00 
                 20.47 
                 15 
                 1 
                 49.27 
                 43.70 
                 0.9 
                 95 
                 0 
                 0 
               
               
                 136 
                 o-xylene 
                 16.00 
                 16.34 
                 15 
                 1 
                 49.91 
                 39.91 
                 0.9 
                 94.6 
                 0 
                 0 
               
               
                 137 
                 o-xylene 
                 19.99 
                 20.98 
                 15 
                 1 
                 52.72 
                 38.22 
                 0.7 
                 97.5 
                 0 
                 0 
               
               
                 138 
                 o-xylene 
                 16.00 
                   
                 15 
                 1 
                 52.92 
                 37.75 
                 0.7 
                 94.5 
                 0 
                 0 
               
               
                 139 
                 o-xylene 
                 15.97 
                 16.13 
                 15 
                 1 
                 53.37 
                 42.58 
                 0.8 
                 94.9 
                 0 
                 0 
               
               
                 140 
                 o-xylene 
                 19.98 
                 21.15 
                 15 
                 1 
                 56.46 
                 31.86 
                 0.7 
                 95.5 
                 0 
                 0 
               
               
                 141 
                 o-xylene 
                 18.00 
                   
                 25 
                 1 
                 56.53 
                 0.00 
                 1.45 
                 95 
                 0.3 
                 0.1 
               
               
                 142 
                 o-xylene 
                 17.81 
                 18.40 
                 15 
                 1 
                 64.50 
                 30.28 
                 0.6 
                 94.1 
                 0 
                 0.1 
               
               
                 143 
                 o-xylene 
                 18.07 
                 18.52 
                 15 
                 1 
                 66.71 
                 28.69 
                 0.7 
                 95.3 
                 0.8 
                 0 
               
               
                 144 
                 o-xylene 
                 15.09 
                   
                 10 
                 1 
                 67.02 
                 27.36 
                 1.1 
                 96.4 
                 0.3 
                 0 
               
               
                 145 
                 o-xylene 
                 15.09 
                   
                 15 
                 1 
                 67.80 
                 49.81 
                 0.8 
                 96.15 
                 0.8 
                 0 
               
               
                 146 
                 o-xylene 
                 18.11 
                   
                 25 
                 1 
                 68.12 
                 0.00 
                 0.8 
                 88.7 
                 5.1 
                 0.2 
               
               
                 147 
                 o-xylene 
                 16.60 
                   
                 15 
                 4 
                 68.19 
                 32.78 
                 1 
                 90.35 
                 5.8 
                 0 
               
               
                 148 
                 o-xylene 
                 15.09 
                   
                 15 
                 4 
                 69.15 
                 0.00 
                 0.7 
                 89.65 
                 6 
                 0 
               
               
                 149 
                 o-xylene 
                 20.00 
                 20.15 
                 15 
                 2 
                 69.96 
                 22.23 
                 0.6 
                 89.15 
                 6.45 
                 0 
               
               
                 150 
                 o-xylene 
                 16.60 
                   
                 15 
                 1 
                 71.08 
                 27.89 
                 0.9 
                 92.15 
                 3.65 
                 0 
               
               
                 151 
                 o-xylene 
                 14.86 
                   
                 15 
                 1 
                 73.29 
                 21.22 
                 0.6 
                 90.6 
                 4.3 
                 0.1 
               
               
                 152 
                 o-xylene 
                 16.60 
                   
                 15 
                 1 
                 73.30 
                 0.00 
                 0.9 
                 90.75 
                 5.15 
                 0.1 
               
               
                 153 
                 ODCB 
                 18.00 
                   
                 15 
                 1 
                 57.08 
                 0.00 
                 2.4 
                 95.2 
                 0.2 
                 0.1 
               
               
                 154 
                 p-xylene 
                 18.11 
                   
                 25 
                 1 
                 59.95 
                 36.79 
                 0.9 
                 90.1 
                 5.1 
                 0.1 
               
               
                 155 
                 p-xylene 
                 15.09 
                   
                 15 
                 1 
                 65.92 
                 34.96 
                 0.6 
                 88.5 
                 5.15 
                 0 
               
               
                 156 
                 p-xylene 
                 14.98 
                   
                 15 
                 4 
                 78.06 
                 21.37 
                 0.9 
                 87.9 
                 7.9 
                 0 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                   
                 TABLE IV 
               
             
            
               
                   
                   
               
               
                   
                 Product Analysis 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Stg Mtl. 
                   
                 Loading 
                 Filt Temp 
                 Stir time 
                 Recovery 
                 Isomer (3) 
                 Product 
                 2′-nitro 
                 6′-nitro 
               
               
                 Exp. 
                 Str % 
                 Solvent 
                 (%) 
                 (° C.) 
                 (hr) 
                 (%) 
                 (%) 
                 (%) 
                 (%) 
                 (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 157 
                   
                 2-Chlorotoluene 
                 15 
                 15 
                 1 
                 70 
                 1 
                 95.4 
                 0 
                 0.9 
               
               
                 158 
                   
                 AcOH/water 
                   
                   
                   
                   
                 3 
                 79.7 
                 8.1 
                 1.96 
               
               
                 159 
                 72.8 
                 AcOH/water 
                   
                   
                   
                 96 
                 2.5 
                 78.7 
                 8.7 
                 3.6 
               
               
                 160 
                 72.4 
                 AcOH/water 
                   
                   
                   
                 97.6 
                 3.1 
                 77.0 
                 8.26 
                 3.72 
               
               
                 161 
                   
                 o-xyl/ODCB 95/5 
                 20 
                 25 
                 1 
                 60.6 
                 0.8 
                 92.5 
                 1.6 
                 0 
               
               
                 162 
                   
                 o-xylene 
                 15 
                 25 
                 0.5 
                 48.50 
                 0 
                 90.0 
                 0 
                 0 
               
               
                 163 
                   
                 o-xylene 
                 15 
                 25 
                 1 
                 55 
                 0.72 
                 98.1 
                 0.48 
                 0 
               
               
                 164 
                   
                 o-xylene 
                 20 
                 25 
                 1 
                 70.4 
                 0.71 
                 93.0 
                 5.65 
                 0.16 
               
               
                 165 
                 79.7 
                 o-xylene 
                 12 
                 25 
                 1 
                 68.8 
                 0.5 
                 95.4 
                 2.4 
                 0 
               
               
                 166 
                 79.7 
                 o-xylene 
                 20 
                   
                   
                 78.5 
                 0.4 
                 89.3 
                 6.4 
                 0 
               
               
                 167 
                   
                 o-xylene 
                 25 
                 25 
                 0.5 
                 88 
                 0.6 
                 91.2 
                 6.7 
                 0 
               
               
                 168 
                 78.7 
                 o-xylene 
                 15 
                 25 
                 1 
                 73.8 
                 0.4 
                 91.4 
                 5.95 
                 0 
               
               
                 169 
                 78.7 
                 o-xylene 
                 12 
                 25 
                 1 
                 68 
                 0.3 
                 90.7 
                 5.2 
                 0 
               
               
                 170 
                   
                 o-xylene 
                 20 
                 25 
                 1 
                 72.2 
                 0.3 
                 90.3 
                 6.1 
                 0 
               
               
                 171 
                   
                 o-xylene 
                 20 
                 25 
                 1 
                 88.7 
                 0 
                 89.5 
                 5.7 
                 0 
               
               
                 172 
                   
                 o-xylene 
                 20 
                 5 
                 0.5 
                 72.2 
                 1.6 
                 88.9 
                 4.4 
                 0.3 
               
               
                 173 
                   
                 o-xylene 
                 12 
                 5 
                 1 
                 61.3 
                 1.3 
                 94.1 
                 0 
                 0 
               
               
                 174 
                   
                 o-xylene 
                 15 
                 5 
                 1 
                 66 
                 1.2 
                 92.0 
                 3.1 
                 0 
               
               
                 175 
                   
                 o-xylene 
                 20 
                 25 
                 0.5 
                 83.6 
                 0.6 
                 90.8 
                 6.5 
                 0 
               
               
                 176 
                   
                 o-xylene 
                 18 
                 25 
                 0.5 
                 58 
                 0.5 
                 94.4 
                 0 
                 0 
               
               
                 177 
                   
                 o-xylene 
                 15 
                 25 
                 1 
                 77.7 
                 0.5 
                 94.4 
                 3.7 
                 0 
               
               
                 178 
                   
                 o-xylene 
                 20 
                 25 
                 1 
                 58 
                 0.5 
                 95.1 
                 0 
                 0 
               
               
                 179 
                   
                 o-xylene 
                 18 
                 25 
                 1 
                 54.3 
                 0.5 
                 94.9 
                 0 
                 0 
               
               
                 180 
                   
                 o-xylene 
                 20 
                 5 
                 1 
                 88.8 
                 1.9 
                 88.7 
                 7.6 
                 0 
               
               
                 181 
                   
                 o-xylene 
                 30.8 
                 5 
                 1 
                 83.8 
                 1.7 
                 87.6 
                 6.4 
                 0.1 
               
               
                 182 
                   
                 o-xylene 
                 30 
                 5 
                 0.5 
                 78.5 
                 1.6 
                 87.6 
                 6.3 
                 0.2 
               
               
                 183 
                   
                 o-xylene 
                 18 
                 5 
                 1 
                 68.1 
                 1.5 
                 89.2 
                 5 
                 0 
               
               
                 184 
                   
                 o-xylene 
                 25.2 
                 5 
                 1 
                 80.8 
                 1.6 
                 87.7 
                 6.5 
                 0 
               
               
                 185 
                   
                 o-xylene 
                 20 
                 5 
                 1 
                 74.6 
                 1.5 
                 87.5 
                 5.9 
                 0.3 
               
               
                 186 
                   
                 o-xylene 
                 15 
                 5 
                 1 
                 81.8 
                 1.6 
                 89.4 
                 6.1 
                 0 
               
               
                 187 
                   
                 o-xylene 
                 12.2 
                 5 
                 1 
                 77.7 
                 1.5 
                 90.8 
                 4.5 
                 0 
               
               
                 188 
                 20.4 
                 o-xylene 
                 21 
                 4 
                   
                 58 
                 1.4 
                 88.2 
                 6.1 
                 0.2 
               
               
                 189 
                 13.6 
                 o-xylene 
                 15 
                 25 
                   
                 51 
                 0.7 
                 95.7 
               
               
                 190 
                 13.6 
                 o-xylene 
                 15 
                 25 
                   
                 53 
                 0.6 
                 96.2 
               
               
                 191 
                 13.6 
                 o-xylene 
                 18 
                 25 
                   
                 64 
                 0.6 
                 96.5 
               
               
                 192 
                 13.6 
                 o-xylene 
                 21 
                 25 
                   
                 67.1 
                 0.7 
                 93.2 
                 2.5 
               
               
                 193 
                 13.6 
                 o-xylene 
                 18 
                 25 
                   
                 64 
                 0.6 
                 96.3 
                 0 
               
               
                 194 
                 13.6 
                 o-xylene 
                 15 
                 25 
                   
                 58 
                 0.9 
                 96.3 
                 0 
               
               
                 195 
                   
                 ODCB 
                 16.5 
                 15 
                 1 
                 76 
                 0.6 
                 96.8 
                 0.45 
                 0 
               
               
                 196 
                   
                 ODCB 
                 18 
                 15 
                 1 
                 83 
                 0.7 
                 95.1 
                 1.5 
                 0 
               
               
                 197 
                   
                 ODCB 
                 20 
                 15 
                 1 
                 79 
                 0.6 
                 90.6 
                 5.4 
                 0.15 
               
               
                 198 
                   
                 ODCB 
                 18 
                 15 
                 1 
                 76 
                 0.6 
                 91.2 
                 3.75 
                 0 
               
               
                 199 
                   
                 ODCB 
                 18 
                 15 
                 2 
                 74 
                 0.9 
                 91.1 
                 2.4 
                 0 
               
               
                 200 
                   
                 ODCB 
                 18 
                 15 
                 1 
                 82.7 
                 0.7 
                 94.1 
                 4.9 
                 0 
               
               
                 201 
                   
                 ODCB 
                 18 
                 15 
                 6.25 
                 82.7 
                 0.7 
                 90.1 
                 8.42 
                 0 
               
               
                 202 
                 78.7 
                 ODCB 
                 20 
                 15 
                 1 
                 82 
                 0.6 
                 89.0 
                 6.6 
                 0 
               
               
                 203 
                   
                 ODCB 
                 15 
                 15 
                 1 
                 69.70 
                 0.96 
                 94.5 
                 0 
                 0 
               
               
                 204 
                   
                 ODCB 
                 20 
                 15 
                   
                 77.4 
                 0.7 
                 93.8 
                 3.1 
               
               
                 205 
                 13.6 
                 ODCB 
                 15 
                 15 
                   
                 67 
                 1.4 
                 96.2 
                 0 
               
               
                 206 
                 13.6 
                 ODCB 
                 15 
                 15 
                   
                 75.5 
                 1.3 
                 96.5 
                 0 
               
               
                 207 
                 13.6 
                 ODCB 
                 15 
                 15 
                   
                 78.6 
                 1.3 
                 93.0 
                 2.5 
               
               
                 208 
                 62.8 
                 tech xylene 
                 11.8 
                 30 
                 4 
                 40.1 
                 0.3 
                 89.4 
                 0.96 
                 0 
               
               
                 209 
                   
                 tech-xylene 
                 17 
                 30 
                   
                 85.1 
                 0.5 
                 92.4 
                 5.75 
               
               
                 210 
                   
                 tech-xylene 
                 17 
                 19 
                   
                 89.8 
                 0.6 
                 90.9 
                 6.7 
               
               
                 211 
                 (67.9) 
                 tech-xylene 
                 16.5 
                 25 
                 0.25 
                 59 
                 0.5 
                 85.6 
                 6.41 
                 0. 
               
               
                 212 
                 (67.9) 
                 tech-xylene 
                 15 
                 30 
                 4 
                 55.8 
                 0.4 
                 86.5 
                 5.3 
                 0 
               
               
                 213 
                 (62.8) 
                 tech-xylene 
                 15 
                 28 
                 0.5 
                 50.4 
                 0.5 
                 87.2 
                 5.3 
                 0 
               
               
                 214 
                 (62.8) 
                 tech-xylene 
                 15 
                 26 
                 0.75 
                 51.2 
                 0 
                 79.1 
                 4.4 
                 0 
               
               
                 215 
                   
                 tech-xylene 
                 12 
                 25 
                   
                 86.9 
                 0.4 
                 94.0 
                 4.74 
                 0 
               
               
                 216 
                   
                 tech-xylene 
                 15 
                 25 
                 1 
                 63 
                 0.7 
                 90.5 
                 7.08 
                 0 
               
               
                 217 
                   
                 tech-xylene 
                 15 
                 25 
                 0.5 
                 71.2 
                 0 
                 86.8 
                 8.9 
                 0 
               
               
                 218 
                 83.3 
                 tech-xylene 
                 25 
                 25 
                   
                 92 
                 0.6 
                 93.0 
                 6 
               
               
                 219 
                 13.6 
                 tech-xylene 
                 20 
                   
                   
                 95.6 
                 5.18 
                 75.3 
                 7.24 
                 4.32 
               
               
                 220 
                 75.3 
                 tech-xylene 
                 20 
                 25 
                 0.5 
                 68 
                 0.6 
                 90.7 
                 8.6 
                 0 
               
               
                 221 
                 13.6 
                 tech-xylene 
                 20 
                   
                   
                 93.6 
                 4.95 
                 73.6 
                 7.92 
                 4.03 
               
               
                 222 
                 73.6 
                 tech-xylene 
                 20 
                 25 
                   
                 67.7 
                 0.7 
                 95.4 
                 4.2 
                 0 
               
               
                 223 
                 13.6 
                 tech-xylene 
                 20? 
                 25? 
                   
                 75.5 
                 0.6 
                 91.1 
                 6 
                 0 
               
               
                 224 
                   
                 xyls/ACN 95/5 
                 17 
                 25 
                 1.5 
                 22.2 
                 0.4 
                 92.4 
                 1.1 
                 0 
               
               
                   
               
            
           
         
       
     
     The effectiveness of various crystallisation solvents can be seen from Tables I and II by a comparison of, for example, the results for Experiments Nos. 3, 11, 24, 31, 38, 41, 54, 60, 88 and 112 for which the solvents are 2-chlorotoluene, 2-fluorotoluene, benzotrifluoride, bromobenzene, monochlorobenzene, m-dichlorobenzene, o-xylene, o-dichlorobenzene, p-xylene and 4-chlorotoluene respectively. It can be seen that for all of these solvents it is possible to obtain the required product in a yield of between about 65% and 82% and at a purity of between about 81% and 96% depending upon the purity of the starting material and the crystallisation conditions employed. As briefly mentioned above, the proportion of the 2′-nitro isomer in the purified product is of critical importance since this is particularly difficult to separate from the required product and it can be seen from the experiments identified above that recrystallisation using o-xylene results in a particularly low content of the 2′-nitro isomer in the product mix. Other solvents which give low proportions of the 2′-nitro isomer include benzotrifluoride, monochlorobenzene and o-dichlorobenzene. 
     The beneficial effect of reduced loading of the crystallisation solution is apparent from the results presented in Tables I to IV. For example, in Table II, Experiments 104, 105, 107, 111, 114 and 116 all use 4-chlorotoluene as crystallisation solvents with loadings of 6.15, 8.19, 10.23, 12.27, 14.31 and 16.34 respectively. The yield of product increases as the loading increases from 52.9% at a loading of 6.15% to 77.7% at a loading of 16.34%. However, the purity of the product also decreases, particularly for loadings of greater than 10% and, in particular, the content in the product of the 2′-nitro isomer increases with loading. It is clear from the results shown for this series of experiments that the yield and product quality are optimised at a loading of between 8 and 12% when the crystallisation solvent is 4-chlorotoluene. 
     A similar effect can be seen from Table IV taking the results of Experiments 173 and 174 which both use o-xylene as solvent and have crystallisation solvent loadings of 12 and 15% respectively. Once again, it can be seen that, although the yield of product increases across this series from 61.3% to 66%, the purity of the product deteriorates from 94.1% to 92%. If these results are compared with those of Experiment 172, which was carried out under similar conditions except that the stir time was shorter, it can be seen that increasing the loading to 20% caused a decrease in the purity of the product and, in addition, an increase in the amount of 2′-nitro isomer from 0 to 4.4%. This shows that the increase in loading is significant because the shortened stir time tends to increase the quality of the product. Thus, for o-xylene, it appears that the optimum loading of the crystallisation solution is between about 12 and 15%. 
     The effect of loading is also demonstrated by taking the results of Experiments 195 to 197 of Table IV in which the solvent is o-dichlorobenzene. Here, the yield varies less than with some other solvents as the loading of the crystallisation solution is increased from 16.5 to 20% but the purity of the product is significantly affected, deteriorating from 96.8% to 90.6% with the amount of 2′-nitro isomer increasing from 0.45 to 5.4%. For this solvent, therefore, it would appear that the optimum crystallisation solution loading is between about 16 and 20%. 
     Thus, in summary, whatever the solvent, an increase in loading of the crystallisation solution always has the effect of decreasing the percentage of the required product and increasing the percentage of the 2′-nitro isomer in the final mixture obtained. This is significant because of the difficulty in separating the 2′-nitro isomer from the required 4′-nitro product. It is also clear that the optimum product loading may vary depending upon the particular crystallisation solvent which is used. In all cases, however, the loading of the crystallisation solvent should be kept below 25%. 
     Tables I to IV also demonstrate the effect of temperature on the purification process of the present invention. For example, in Table I, Experiments 25 and 26 were carried out in the same solvent, benzotrifluoride, and under similar conditions except that the filtration temperature was 15° C. for Experiment 25 and 10° C. for Experiment 26. Other groups of experiments which show the effect of a change in filtration temperature are Experiments 33 and 34, where the solvent was m-chlorobenzene, 54, 55 and 52 which used o-xylene as solvent, 86 and 88 using p-xylene; and 123 and 125 using m-chlorobenzene. In all of these groups of experiments except for the group using o-xylene as solvent, an increase in the filtration temperature led to a decrease in yield but also to a slight increase in the amount of 2′-nitro impurity present in the product. The results using o-xylene were particularly satisfactory because, with this solvent, a decrease in the filtration temperature used led not only to an increase in the product yield but also to a decrease in the amount of 2′-nitro impurity. Thus o-xylene is a particularly useful solvent for use in the process of the present invention. 
     The effect of prolonged stirring of the crystallisation mass can also be seen from Tables I to IV. In particular, Experiment 145 of Table 3 shows that after stirring for one hour a crystallisation mass in which the solvent is o-xylene and the filtration temperature is 15° C., a product of 96.15% purity containing 0.8% of the 2′-nitro isomer was obtained in 67% yield. However, when the same mixture was stirred for four hours (Experiment 148), the yield increased slightly to 69% but the product was only 89.65% pure and contained 6% of the 2′-nitro isomer. 
     EXAMPLE 3 
     Deposition of 2′-nitro Isomer from Recrystallisation Filtrates 
     19.4 g of 77% strength Acifluorfen was recrystallised from o-xylene to give a 63% recovery of Acifluorfen of 91.3% strength and 5.1% 2′-nitro isomer content. On standing for several days, the filtrates deposited a solid which was recovered and analysed. The solid was 71.7% Acifluorfen and 24% 2′-nitro isomer. 
     EXAMPLE 4 
     Telescoped Nitration and Purification Using 1,2-Dichlorobenzene 
     190 g of crude 5-(2-chloro-α,α,α,-trifluoro-4-tolyloxy)-benzoic acid (strength 84.2%), 754 g 1,2-dichloroethane and 87.8 g acetic anhydride were charged to a stirred reactor. The mixture was heated to 50° C. to produce a solution, then cooled to 10-15° C. 131 g Mixed acid (33.3% nitric acid, 66.7% sulphuric acid) was added evenly over 2 hours at 10-15° C. After mixed acid addition, the reaction mass was held at 10° C. for 1 hour and then quenched with 15 g water. The mixture was heated to 70° C. and the acid layer was separated. The solvent layer was given two washes (210 g) with 5% sodium chloride solution at 70° C. to remove acetic acid. Water (194 g) was added and the 1,2-dichloroethane was removed by distillation whilst returning the water phase to the reactor. To the resulting viscous oil/water mixture was added 1,2-dichlorobenzene (550 g) and the aqueous layer was separated off at 70° C. The solvent solution was given a water wash, separated and dried by azeotropic distillation. The resulting solution was cooled at 20° C. per hour to 15° C. and seeded with Acifluorfen at 50° C. The crystallisation mass was stirred for 1 hour at 15° C., filtered and dried under reduced pressure before oven drying to remove residual solvent. Yield of 5-(2-chloro-α,α,α,-trifluoro-4-tolyloxy)-2′-nitro-benzoic acid, 62.7% of theory. The product had the following composition: 
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 Acifluorfen 
                 90.1% 
               
               
                   
                 2′-nitro 
                 4.6% 
               
               
                   
                 6′-nitro 
                 0.2% 
               
               
                   
                 others 
                 2.6% 
               
               
                   
                   
               
            
           
         
       
     
     EXAMPLE 5 
     Effect of Stir Time on the Quality of Product from Recrystallisation of Acifluorfen 
     The nitration, washing and solvent removal were carried out as in Example 4. o-Xylene (510 g) was added to the crude Acifluorfen melt and the solution was dried and crystallised as in Example 4. Aliquots of about 130 g were removed from the crystallisation mass, after cooling to 15° C., at 1 hour intervals to determine the effect of stir time on product quality. The samples were filtered, pulled dry, oven dried and analysed and the results are shown in Table V below. 
     
       
         
           
               
               
               
             
               
                 TABLE V 
               
               
                   
               
               
                 Time at 15° C. 
                 Acifluorfen strength % 
                 2′-nitro content % 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 1 hour 
                 87 
                 6.48 
               
               
                 2 hour 
                 82.5 
                 7.63 
               
               
                 3 hour 
                 85.9 
                 8.35 
               
               
                 4 hour 
                 86.7 
                 8.52 
               
               
                 5 hour 
                 85.9 
                 9.32 
               
               
                 6 hour 
                 84.7 
                 9.36 
               
               
                   
               
            
           
         
       
     
     EXAMPLE 6 
     Telescoped Nitration and Purification Using o-Xylene 
     433.2 g of a solution of the sodium salt of crude 5-(2-chloro-α,α,α-trifluoro-4-tolyloxy)-benzoic acid (strength 36.2% expressed as free acid) and 754 g 1,2-dichloroethane was charged to a stirred reactor and heated to 60° C. Sulphuric acid was added to adjust the pH to 2.0. The aqueous layer was separated and the solvent layer was dried by azeotropic distillation. 87.8 g Acetic anhydride was added at 50° C. and the solution was nitrated and worked up to give the crude product as a molten oil/water mixture as in Example 4. To this mixture was added 60.9 g of 47% strength sodium hydroxide solution at 50° C. to adjust the pH to &gt;10. Traces of 1,2-dichloroethane were removed by distillation and o-xylene (833 g) was added followed by sulphuric acid (53 g) to adjust the pH to 2.0. After a short period of stirring, the aqueous layer was separated off whilst the mixture was at &gt;70° C. The solvent layer was dried by azeotropic distillation, then cooled to 15° C. as described in Example 4. The Acifluorfen product was recovered by filtration and dried. 
     Yield of 5-(2-chloro-α,α,α-trifluoro-4-tolyloxy)-2′-nitro-benzoic acid: 
     Nitration 83% theory 
     Recrystallisation 70.7% theory 
     Overall 58.8% theory. 
     The product had the following composition: 
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 Acifluorfen 
                 97.0% 
               
               
                   
                 2′-nitro 
                 0.6% 
               
               
                   
                 6′-nitro 
                 0.1% 
               
               
                   
                 Others 
                 2.3% 
               
               
                   
                   
               
            
           
         
       
     
     EXAMPLE 7 
     Extraction of Crude Acifluorfen Acid with Aqueous Acetic Acid) 
     21.7 g of Acifluorfen (68.9% strength), acetic acid and 10.9 g water were mixed and stirred at 22° C. for 2 hours. The slurry was filtered and the solid product given a small wash with 50% aqueous acetic acid. The product was oven dried at 80° C. The recovery of Acifluorfen was 95.9% and the product had an Acifluorfen strength of 79.2%.