PREPARATION OF CHLOROBENZOTRIFLUORIDE COMPOUNDS

Abstract: Chlorobenzotrifluoride compounds, especially 3,4,5-tri­ chlorobenzotrifluoride, are obtained by replacement of at least one m-nitro group in a nitrobenzotrifluoride by chlorine using chlorine gas in the presence of a catalyst comprising a metal salt and a sulphur compound.

Description: PREPARATION OF CHLOROBENZOTRIFLUORIDE COMPOUNDS This invention relates to a process for the replacement of aromatic nitro groups by chlorine and more particularly to a process for the preparation of chlorobenzotrifluoride compounds, useful as chemical intermediates in the synthesis of agricultural products, e.g. herbicides, from nitrobenzotrifluorides. According to the invention, there is provided a process f r the replacement by chlorine of at least one nitro group in a compound of the formula (I): EMI1.1 in which X is hydrogen, chloro or nitro, and Y and Z are independently hydrogen or chloro, the process comprising treating the compound (I) with molecular chlorine in the presence of a catalyst comprising a metal salt and a sulphur compound. When X is nitro, one or both nitro groups are replaced by chlorine. Examples of compound (I) are 4-chloro-3-nitrobenzotrifluoride from which 3,4-dichlorobenzotrifluoride can be obtained, and 4-chloro-3 , 5-dinitrobenzotrifluoride from which 3, 4-dichloro-5- nitrobenzotrifluoride, 3,4,5-trichlorobenzotrifluoride and 2,3,4,5-tetrachlorobenzotrifluoride can be obtained. The catalyst used in the process of the invention preferably comprises a Friedel-Crafts type of catalyst and a divalent sulphur compound. Generally, those Friedel-Crafts catalysts which are most active in alkylation reactions (see, e.g. Friedel-Crafts Chemistry, Olah, Wiley & Sons [1973J pp.33-34) are most suitable for use in the present invention. Thus ferric chloride and, especially, aluminium trichloride are very effective while stannic chloride, titanium tetrachloride and zinc chloride are less effective. Suitable sulphur compounds include inorganic sulphur compounds such as sulphur monochloride, and organic sulphur compounds such as thiophenol, p-(thio)cresol, dodecyl mercaptan, thiobenzoic acid, diphenyl disulphide and 1,2-bis(phenylthio)ethane. Of these, the last is very efficient and selective (e.g. chlorination of 4-chloro-3,5-dinitrobenzotrifluoride proceeds to 90% completion with very little formation of the tetrachloro compound), but not readily available. Diphenyl disulphide is efficient but not so selective. Thiophenol is, commercially, the most favoured, the substituted thiophenols, dodecyl mercaptan and thiobenzoic acid generally giving slower reactions. Sulphur monochloride is low boiling and tends to "flash-off" at preferred temperatures of reaction. Diphenyl sulphide is an example of an organic sulphur compound which is less effective. The amount of each component of the catalyst present may be any amount which gives a catalytic effect. It will vary widely depending on the particular combination of catalysts selected. Generally, it will be in the range of from 0.1 to 10% or more by weight of compound (I), usually in the range of from 0.3 to 5%. In the absence of one or both components of the catalyst, reaction is very slow if it occurs at all. The process of the invention may be carried out under a wide range of temperatures and pressures depending on the particular substrate used. Preferably it is conducted in the liquid phase at atmospheric pressure at a temperature up to 2200C, preferably above 1500C and especially in the range of from 180 to 2100 C. In practice, compound (I) is melted or, if this is not practicable, dissolved in an inert solvent such as a chlorinated hydrocarbon and the components of the catalyst mixed in. The mixture is heated to the desired temperature and chlorine gas passed through until reaction is complete. Completion of reaction may be determined by glc analysis of samples of the reaction mixture taken periodically. The product or mixture of products may be separated by fractional distillation. As a guide, the rate at which chlorine is passed through the reaction mixture may be in the range of from 0.0001 to 0.1 mols of chlorine per mol of starting material per minute. However, it has been found advantageous, with respect to product yield, if the rate is kept below 0.01 mol Cl2/mol/minute and preferably below 0.001, typically 0.0002 to 0.0006 mol Cl 2/mol/minute. The starting materials of the formula (I), which are known compounds, may be obtained by chlorination, as required, of benzotrifluoride to form 4-chlorobenzotrifluoride followed by nitration. 3-nitrobenzotrifluorides substituted with chlorine in the 5-position may be obtained by replacement of one nitro group from a 3,5-dinitrobenzotrifluoride by the process of the invention by working, for example, at lower temperatures. Benzotrifluoride itself is obtained from benzotrichloride by reaction with e.g. hydrogen fluoride and antimony pentafluoride. Benzotrichloride is obtained by the continued action of chlorine on boiling toluene in the presence of light. The following compounds of the formula (I) are registered in Chemical Abstracts, the Registry Numbers being given in parentheses: 1-nitro-3-trifluoromethylbenzene [98-46-4] 1-chloro-2-nitro-4-trifluoromethylbenzene [121-17-5] 1-chloro-2,6-dinitro-4-trifluoromethylbenzene [393-75-9] 1, 2-dichloro-3-nitro-5-trifluoromethylbenzene [657-02-03] 1, 3-dichloro-2, 4-dinitro-6-trifluoromethylbenzene [29091-09-6]. The process of the invention facilitates the preparation of chlorobenzotrifluoride compounds difficult to synthesise by other means because of the particular positioning of the chlorine substituents. The invention is illustrated by the following Examples in which the composition of the products is estimated by area normalisation of a gas chromatographic trace. Example 1 Chlorination of 4-chloro-3,5-dinitrobenzotrifluoride 4-Chloro-3,5-nitrobenzotrifluoride (135.25g : 0.5 mole) was charged to a 150ml four-necked flask fitted with paddle agitator, thermometer, glass tube gas inlet and " diameter glass column packed with glass helices and topped with a condenser. The flask was heated to 709C to melt the contents, distilled sulphur monochloride (3.8g) and ferric chloride (4.58g) were added and the temperature raised to 180"C. Chlorine gas was passed through the flask contents for a total of 17 hours. The temperature was raised to 2000C after four hours and maintained between 196 and 2000C for the remaining time. The progress of reaction was monitored by glc analysis of samples taken approximately every hour (5' 10% OV 210 column; 110-1800C at 1500/mien; carrier gas approx. 50ml/min.). The final analysis showed the reaction mixture to contain 8% unreacted 4-chloro-3,5-nitrobenzotrifluoride, 19% 3,4-dichloro5-nitrobenzofluoride, 63% 3,4,5-trichlorobenzotrifluoride and 10% 2,3,4,5-tetrachlorobenzotrifluoride. Example 2 Chlorination of 4-chloro-3-nitrobenzotrifluoride Chlorine gas was passed at 20 to 30ml/min. through a heated mixture of 4-chloro-3-nitrobenzotrifluoride (67.65g; 0.3 mole), sulphur monochloride (2.29g) and ferric chloride (2.75g) for a total of 13 hours. The temperature of the mixture was maintained at 118 to 1200C for 6 hours, 133 to 137 C for 4 hours and 152 to 15600 for the remaining time. Final analysis of the reaction mixture by glc showed it to contain 8.2% 3,4-dichlorobenzotrifluoride, 1.6% 3,4-dichloro-5nitrobenzotrifluoride and 90.1% of unreacted 4-chloro-3-nitrobenzotrifluoride. Examples 3 to 9 Chlorination of 4-chloro-3, 5-dinitrobenzotrifluoride These examples illustrate the use of different sulphur compounds and the use of different metal salts with one of those compounds. All experiments were carried out as generally described below and the results are displayed in Table 1. Apparatus - a 150ml 4 neck brown flask fitted with PTFE paddle agitator, thermometer, plain glass tube for gas inlet, a ¸" diameter glass column packed with 6" of glass helices leading to a distillation head condenser and receiver. The flask was heated with an oil bath. Procedure - 4-chloro-3,5-dinitrobenzotrifluoride (135.25g = 0.5g.mol) was charged to the flask and heated to 700C at which temperature it melted. The agitator was started, the sulphur compound charged followed by the metal salt. The mixture was heated to the desired temperature and chlorine addition commenced. The chlorine flow rate was not monitored in these experiments but was of the order of O.5g/min. The experiments were shut down at the end of each working day and excess chlorine was removed by bubbling nitrogen through the reaction mass for 30 minutes. Table 1 EMI6.1 <tb> <SEP> OH <SEP> N <SEP> EsS%. <SEP> l.S <SEP> A <tb> <SEP> zip <SEP> Temp <SEP> SUIUfl <SEP> COXPOL1?tfl <SEP> MAL <SEP> SALT <SEP> NO <SEP> or3 <SEP> ;a <SEP> 3Cl <SEP> CF <SEP> COMHZ2S <tb> <SEP> No. <SEP> f;;4 <SEP> rir <SEP> Aaount <SEP> e <SEP> Cl <SEP> CF <tb> Formula <SEP> a <SEP> s/s.mo <SEP> 5 <SEP> X <SEP> , <SEP> NO <tb> <SEP> an <SEP> pq <SEP> f3 <SEP> z <SEP> % <SEP> z3.7/ <tb> <SEP> 3 <SEP> aoo <SEP> 3o:1/ <SEP> A1013 <SEP> 0.028 <SEP> 13 <SEP> 13 <SEP> a <SEP> After <SEP> 14 <SEP> bra <SEP> a <SEP> smaLl <SEP> amount <tb> <SEP> or <SEP> tetrachiorinated <SEP> rroduat <tb> <SEP> was <SEP> detected. <SEP> After <SEP> P <SEP> bra <tb> <SEP> ts <SEP> B,g <SEP> - <SEP> dtd <SEP> not <SEP> chanse <tb> <SEP> after <SEP> a <SEP> furthor <SEP> 4 <SEP> ,,s <tb> <SEP> 4 <SEP> aoo <SEP> on <SEP> 3.3/ <SEP> ALOl <SEP> 3.7/ <SEP> 13 <SEP> a4 <SEP> 38 <SEP> - <SEP> After <SEP> 14 <SEP> bra <SEP> TCDTF <SEP> 37% <SEP> and <tb> 3. <SEP> 0.028 <SEP> 3 <SEP> 0.028 <SEP> reactton <SEP> etopped. <SEP> Extra <tb> <SEP> R <SEP> added <SEP> and <SEP> after <tb> <SEP> 10 <SEP> bra <SEP> reacton <SEP> stopped <SEP> at <tb> <SEP> 38e' <SEP> TcoTF. <SEP> Addton <SEP> or <tb> <SEP> a <SEP> cotalyet <SEP> save <SEP> no <tb> <SEP> sprovaaent. <tb> <SEP> 3 <SEP> 200 <SEP> dodecyl <SEP> an <SEP> 3.3/ <SEP> AlOl <SEP> 3.7/ <SEP> a9 <SEP> 33 <SEP> - <SEP> The <SEP> wasthe <SEP> reault <SEP> after <tb> <SEP> o.028 <SEP> 0.028 <SEP> 18 <SEP> bra <SEP> cbloynation. <SEP> The <tb> <SEP> reaction <SEP> wac <SEP> vary <SEP> slow <tb> <SEP> compared <SEP> wLth <SEP> Example <SEP> 4. <tb> <SEP> 6 <SEP> 200 <SEP> Qooni <SEP> 3.9/ <SEP> AlCI <SEP> 3.7/ <SEP> 11.3 <SEP> 24.3 <SEP> 60.3 <SEP> - <SEP> The <SEP> chlorination <SEP> lasted <tb> <SEP> 0.028 <SEP> ----------- <SEP> -------- <SEP> bre. <SEP> ------ <SEP> appeared <tb> <SEP> to <SEP> be <SEP> similar <SEP> to <SEP> ±rnplo <SEP> 3. <tb> ? <SEP> 200 <SEP> 6.1/ <SEP> AlCl3 <SEP> 3.7/ <SEP> 11 <SEP> ai <SEP> 39 <SEP> 9 <SEP> After <SEP> 13 <SEP> bra <SEP> tbe <SEP> TCflTF <SEP> level <tb> <SEP> 0.028 <SEP> 0.028 <SEP> was <SEP> 64iafter <SEP> a <SEP> f'irLhr <SEP> 4 <SEP> bra <tb> <SEP> thia <SEP> bad <SEP> decreased <SEP> to <SEP> 3% <tb> 8 <SEP> ---------------- <SEP> ------------ <SEP> reaction <tb> <SEP> Fe013 <SEP> 4.6/ <tb> <SEP> 117600 <SEP> o.028 <SEP> 0.028 <SEP> At <SEP> 16000 <SEP> still <SEP> vrry <SEP> slow <SEP> but <tb> <SEP> 2 <SEP> bra <SEP> one <SEP> or <SEP> pentachioro <tb> <SEP> derivative <SEP> preoent. <SEP> At <SEP> 17OC <tb> <SEP> for <SEP> furLher <SEP> I <SEP> bra <SEP> 3fa <SEP> tetra <tb> <SEP> 1 <SEP> and <SEP> 7% <SEP> pentacbloro. <tb> <SEP> ( <SEP> aCia <SEP> .9/ <SEP> AlOl <SEP> 3.7/ <SEP> 1 <SEP> 3 <SEP> 90 <SEP> Otbera <SEP> Very <SEP> slow <SEP> reaction <SEP> below <tb> <SEP> 180 <SEP> 0.028 <SEP> 0.028 <SEP> a <SEP> 6.0 <SEP> 190C. <SEP> At <SEP> 1900C <SEP> reaction <tb> <SEP> g <SEP> completed <SEP> after <SEP> 26 <SEP> bra. <tb> Example 10 Chlorination of 4-chloro-3, 5-dinitrobenzotrifluoride using a slow chlorine addition 4-chloro-3,5-dinitrobenzotrifluoride (1082g : 4.0g.mol) was charged to a 1000ml reactor fitted with a two tier turbine agitator, thermometer, glass tube gas inlet and set for distillation via a water cooled condenser to a receiver. The flask was heated to 70"C to melt the contents, 1,2-bis(phenylthio)ethane (8.0g) and aluminium chloride (4.lg) were added and the temperature raised to 2000C. Chlorine gas, at a rate of 0.12g/min, was passed through the flask contents for a total of 97 hours. The progress of the reaction was monitored by G.L.C. analysis (5' 10% OV 210 column; 110-1800C at 15 C/min; carrier gas approx. 50mljmin.). The final analysis showed the reaction mixture to contain no unreacted starting material, 1X 3,4-dichloro-5-nitrobenzotrifluoride and 98.7% 3,4,5-trichlorobenzotrifluoride. The reaction mixture was cooled, degassed by passing nitrogen through it and screened. The product was washed three times with 5% wt/wt aqueous caustic soda and then washed alkali free with water. Weight yield = 920.2g Strength = 98.7% = 91.0% Theory yield. Examples 11-20 Example 10 was repeated except that the type of sulphur compound used and the chlorination times were varied and, in some cases, dried/non-dried methylethylketone (MEK) solvent and anti-corrosion agents were present, as shown in Table 2. Table 2 EMI8.1 Anti-Corrosion <SEP> MEK <SEP> Chlorination <SEP> Wt. <SEP> % <tb> Example <SEP> Sulphur <SEP> Compound <tb> Agent <SEP> (Dried <SEP> - <SEP> Time <SEP> Yield <SEP> Strength <SEP> Theory <SEP> Comments <tb> No. <tb> Type/Amount <SEP> YES <SEP> or <SEP> NO) <SEP> Name <SEP> Wt.(g) <SEP> (hrs.) <SEP> (g) <SEP> % <SEP> Yield <tb> 11 <SEP> Silica <SEP> Gel <SEP> - <SEP> 1,2-bis <SEP> 8.0 <SEP> 97 <SEP> 911 <SEP> 98.1 <SEP> 89.9 <SEP> A <SEP> corrosion <SEP> rate <tb> SD210/21.6g <SEP> (phenylthio) <SEP> on <SEP> soda <SEP> glass <SEP> of <tb> ethane <SEP> 0.175mm/year <SEP> was <tb> observed. <tb> <SEP> Below <SEP> the <SEP> liquor <tb> line <SEP> very <SEP> little <tb> corrosion. <tb> 12 <SEP> MgCl2/43g <SEP> YES <SEP> " <SEP> 8.0 <SEP> 103 <SEP> 538* <SEP> 91.3 <SEP> 49.2 <SEP> No <SEP> corrosion <SEP> was <tb> observed <SEP> on <SEP> soda <tb> glass. <tb> *Some <SEP> mechanical <tb> loss. <tb> 13 <SEP> - <SEP> YES <SEP> " <SEP> 8.0 <SEP> 115 <SEP> 867 <SEP> 89.7 <SEP> 77.9 <SEP> Corrosion <SEP> in <tb> liquor <SEP> 1.0mm/year <tb> Corrosion <SEP> in <tb> vapour <SEP> 1.0 <SEP> mm/year <tb> 14 <SEP> CaCl2/43g <SEP> YES <SEP> " <SEP> 8.0 <SEP> 89 <SEP> 884 <SEP> 91.05 <SEP> 78.0 <tb> 15 <SEP> CaCl2/43g <SEP> NO <SEP> " <SEP> 8.0 <SEP> 90 <SEP> 855 <SEP> 92.75 <SEP> 75.8 <tb> 16 <SEP> - <SEP> - <SEP> Thiophenol <SEP> 3.5 <SEP> 76 <SEP> 903 <SEP> 97 <SEP> 87.8 <SEP> 1.6% <SEP> tetrachlorinated <tb> detected <SEP> in <tb> final <SEP> product <tb> by <SEP> area <tb> normalisation <SEP> of <tb> glc <SEP> trace. <tb> Table 2 (Continued) EMI9.1 Anti-Corrosion <SEP> MEK <SEP> Chlorination <SEP> Wt. <SEP> % <tb> Example <SEP> Sulphur <SEP> Compound <tb> Agent <SEP> (Dried <SEP> - <SEP> Time <SEP> Yield <SEP> Strength <SEP> Theory <SEP> Comments <tb> No. <tb> Type/Amount <SEP> YES <SEP> or <SEP> NO) <SEP> Name <SEP> Wt.(g) <SEP> (hrs.) <SEP> (g) <SEP> % <SEP> Yield <tb> 17 <SEP> - <SEP> - <SEP> Thiobenzoic <SEP> 4.4 <SEP> 93 <SEP> 971 <SEP> 84.6 <SEP> 92.1 <SEP> 1.3% <SEP> tetra <tb> acid <SEP> chlorinated <tb> detected. <tb> 18 <SEP> - <SEP> - <SEP> 4,7-dithia- <SEP> 6.5 <SEP> 101 <SEP> 893 <SEP> 94.45 <SEP> 84.5 <tb> decane <tb> 19 <SEP> - <SEP> - <SEP> 2,2,7,7- <SEP> 6.6 <SEP> 101 <SEP> 694* <SEP> 89.9 <SEP> - <SEP> *Leaking <SEP> flange <tb> tetramethyl- <SEP> on <SEP> reactor. <tb> 3,6-dithiaoctane. <tb> 20 <SEP> - <SEP> - <SEP> Thiocresol <SEP> 4.0 <SEP> 96 <SEP> 901 <SEP> 94.8 <SEP> 85.6 <tb> N.B. In Examples 11 to 13, the agitator speed was 400 rpm. In all subsequent experiments, the agitator speed was 500 rpm.

Claims: CLAIMS 1. A process for the replacement by chlorine of at least one nitro group in a compound of the formula (I): EMI10.1 in which X is hydrogen, chloro or nitro, and Y and Z are independently hydrogen or chloro, the process comprising treating the compound (I) with molecular chlorine in the presence of a catalyst comprising a metal salt and a sulphur compound. 2. A process according to claim 1 in which the catalyst comprises a Friedel-Crafts catalyst and a divalent sulphur compound. 3. A process according to claim 2 in which the Friedel-Crafts catalyst is aluminium trichloride or ferric chloride. 4. A process according to any one of the preceding claims in which the sulphur compound is selected from the group comprising sulphur monochloride, thiophenol, p-(thio)cresol, dodecyl mercaptan, thiobenzoic acid, diphenyl disulphide and 1,2-bis(phenylthio) ethane. 5. A process according to any one of the preceding claims in which the amount of each component of the catalyst present is in the range of from 0.1 to 10X by weight of compound (I). 6. A process according to any one of the preceding claims in which the process is conducted in the liquid phase at atmospheric pressure at a temperature of from 180 to 2100C. 7. A process according to any of the preceding claims in which chlorine gas is passed through a liquid phase containing compound (I) and the catalyst at a rate below 0.001 mol.chlorine/mol.compound (I)/minute. 8. A process according to any one of the preceding claims in which compound (I) is 4-chloro-3,5-dinitrobenzotrifluoride.

Inventors: STOTT, JEFFREY ASHWORTH, TUCKER, ALAN CYRIL
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1984
Main classification: C07C17
IPC codes: C07B61, B01J31, B01J27, C07C201, C07C205, C07C67, C07C17