Title of Invention

"A PROCESS FOR VAPOUR PHASE ALKYLATION REACTION"

Abstract

A process for vapour phase alkylation reaction for selectively forming monoalkylated arylamine, alkylated at para-position, products comprising : i) contacting arylamines with alkylating agent both in vapour phase in presence of highly acidic mesoporous solid catalyst (UDCaT-1) such as herein described ; ii) maintaining the reaction temperature between 150 - 400°C in the tubular flow reactor; iii) recovering the reaction product by conventional methods.

Full Text

This invention relates to improvements in Fnedel-Crafts process and in particular to Friedel-Crafts acylation process and to a process for vapour phase alkylation of aniline using solid acid catalyst This application has been divided out of Patent Application No 3594/DEL/97 dated December 12 1997 The most common method of introducing an alkyl or acyl group in to an organic compound is via the Fnedel-Crafts reaction by using either aluminium chloride in nitrobenzene or boron tnflunde in liquid HF Recently M Masahiro et al have reported the Fnedel-Crafts acylation reaction using the forgoing catalysts on these and various other Lewis acids such as FeCI3 ZnCI2 SnCI2 TiCI4 lnCI4 and SbCI5 and Bronstead acids such as H2SO4 and HCI These Fnedel-Crafts acylation methods suffer from numerous drawbacks including unpredictable regioselectivity the extremely hazardous solvent system and requirements of large amounts of the acid The homogeneous catalysed Fnedel-Crafts acylations require at least 2 moles of a Lewis acid to generate 1 mole of the product posing an enormous catalyst disposal problem Investigation & study on industrially importance Fnedel-Crafts reaction involving acylation of benzene with 4-chlorobenzoyl chloride to give 4-chlorobenzophenone an important intermediate in the formation of cytrazin - a well known pharmaceutical drug related that in use of various known acidic heterogeneous catalysts so that the problem of disposal of waste catalyst after completion of the Fnedel-Crafts reactions could be avoided Since the solid catalysts could be separated and reused thereby making the process clean and more economic However in use of such known heterogeneous catalysts for acylation of benzene with 4-chlorobenzoyl chloride it was found that most of these catalysts were not at all active for this reaction Use of sulphated zirconia has been reported in such reactions but it could not give yields better than those obtained with classical aluminium chloride Aniline is known to be used as a building block for the manufacture of several products useful to the chemical industry Aniline and its alkylated products are highly useful in fine chemical industry especially for the preparation of pharmaceuticals drugs pesticides plastics additives and dyes Conventionally Fnedel-Crafts alkylation reactions are carried out with homogeneous acid catalysts used in the stoichiometric quantities or in excess The economics associated in the separation processes and the present day s stringent environmental concerns on the disposal of spent homogeneous catalysts make it difficult to proceed with them anymore Heterogeneous acid catalysts have been employed in the synthesis of fert-butyl aromatic amines They are usually prepared by reacting aniline over the acid catalysts with pure isobutylene or C4 fraction from naphtha crackers which contains isobutylene under pressures ranging from 300-950 psig (BurgoyneWF and Dixon D D Applied Catalysis 63 (1990) 117 BurgoyneWF and Dixon DD Eur Pat 336 134 (Oct 1989) CA 113(1990) 171653w Frederick Harold H EUR Pat 69 065, (Jan 1983) C 4, 99 (1983) 38176u Lobanova N S and Popov MA Zh Prinkl Khim (Lenmgrade), 43(4) (1970) 938 (Russ) CA 73(1970) 25032g ) Reactions were performed by either co-feeding the arylamme and alkene over the solid catalyst in a fixed - bed reactor or by reacting the reagents and catalyst in a stirred autoclave There are not many reported studies on the use of alcohols other than methanol and ethanol for the alkylation of aniline using heterogeneous acid catalysts The studies on higher alkylation of aniline over heterogeneous solid acid catalysts have been restricted to the use of alkenes rather than alcohols as the alkylating agent Table A gives the different catalyst used in the alkylation of aniline with isobutylene In the presence of acid catalyst tert-butanol cracks into isobutylene and water Isobutylene thus produced reacts in situ with aniline giving different mono-alkylated products like n-fert-butylanihne 2-tert-butylanihne 4-terf-butylaniline and dialkylated products Table A Different Catalysts used for Alkylation of Aniline (Table Removed) TBA = tert- butyl aniline , DTBA = Di-ferf-butyl aniline Bernard Herstein (US Pat 2, 092, 973, (Sep 14, 1937), CA, 31 (1937) 789345) prepared 4-terf-butylaniline by reacting acetanilide with tert-butyl chloride in the presence of anhydrous AICI3 and the resulting 4-tert-butyl acetanilide is separated from the reaction mixture and is deacetylated Alternatively it was also prepared by hydrogenation of the 4-nitro-tert-butyl benzene at atmospheric pressure at 20 °C over 20% Pt-C (Mazitova F N and Paushkin Ya M Doklady Akad Nauk S S S R 125, (1959), 1033-6) It is thus the basic objective of the present invention is to provide a process for carrying out Friedel-Crafts reactions using solid acidic catalysts which would avoid the drawbacks associated with presently known strongly corrosive acidic catalysts used in such reactions discussed hereinbefore Another object of the present invention is to provide a process for carrying out Friedel-Crafts reaction using solid acidic catalysts which would be free of catalyst disposed problems associated with the known art Yet further object of the present invention is directed to a process for Friedel-Crafts acylation reaction which would provide for better yield as compared to known processes of Friedel-Crafts reaction Yet further objective of the present invention is to provide a process for carrying out vapour phase alkylation of aniline using solid acid catalyst which would avoid the drawbacks associated with presently known strongly corrosive acidic catalysts used in such reactions discussed hereinbefore Another objective of the present invention is directed to a process for vapour phas D alkylation of aniline which would provide selectively better monoalkylated product as against prior art processes which give a mixture of ortho-alkylated, N-alkylated, dialkylated along with para-alkylated compounds Another objective of the present invention is directed to a process for vapour phase alkylation of aniline which would provide better para- selectivity as compared to process of aniline alkylation reaction Thus according to one aspect of the present invention there is provided a process for Friedel-Crafts reactions comprising i contacting aromatic compounds with acylatmg/alkylating in presence of highly acidic mesoporous solid catalyst such as hereindescribed , ii maintaining the reaction under stirring at the reaction temp 50-100°C from 30 mms to 6 hours , and iii recovering the reaction product by conventional methods In the process of the invention the catalyst used was UDCaT-1 discussed and defined in our co-pending Ind Pat Appln entitled "A process for preparation of a highly acidic mesoporous solid catalyst" The said catalyst comprised a synergistic combination of sulfated metal oxide and mesoporous geotypes having surface area of 200-500 m2/g pore volume of 0 1 to 0 3 m3/g pore diameter of 25-35°A XRD (20) of 0-3° and Elemental Si in an amount of 50-60% by wt S in an amount of 5-10% by wt and Zr in an amount of 40-50% by wt According to another aspect of the present invention there is provided a process for vapour phase alkylation reaction for selectively forming monoalkylated arylamme, alkylated at para- position, products comprising I) contacting arylamines with alkylating agent both in vapour phase in presence of highly acidic mesoporous solid catalyst such as hereindescnbed , u) maintaining the reaction temperature between 150 - 400 °C in the tubular down fl ">w reactor m) recovering the reaction product by conventional methods iv) using a ratio of the arylamine to alkylating agent between 4 1 to 1 10 In this process arylamine is selected from the group comprising aniline, alkylated anilines, halogenated anilines hydroxylated anilines In this process alkylating agent is selected from a group comprising alkanols with Carbon number from C2 to C16, cylic alcohols such as cyclohexanol and olefins such as ethylene, propylenes, butylenes, isoamylene, cyclohexene, and other a-olefines In the process of the invention the catalyst used is UDCaT-1 discussed and defined in our co-pending Indian Patent Applicationentitled "A process for preparation of a highly acidic mesoporous solid catalyst" The said catalyst comprised a synergistic combination of metal oxide and mesoporous zeotype having surface area of 200-500 m2/g pore volume of 0 1 to 0 3 m3/g pore diameter of 25-35 °A XRD(2)of O-3°and Elemental Si in an amount of 50-60% by wt S in an amount of 5-10% by wt and Zr in an amount of 40-50% by wt EXAMPLES The invention will now be illustrated with the help of Examples The examples are by way of illustration only and not to restrict the invention Example 1 Acylation of benzene with 4-chloro benzoyl chloride in presence of Aluminium chloride i Acylation of benzene with 4-chloro benzoyl chloride in presence of Aluminium chloride The current industrial process empoly Aluminium chloride The reaction has a drawback of being homogeneous and hence the problem of recovery of the catalyst Beside, the amount of the catalyst used is equimolar to the amount of reactant which is very high 90% conversion of 4-chlorobenzoyl chloride to 4-chlorobenzophenone takes place in 4 h at 65-70°C Reported reaction yield is 70% n Tanabe K, Yamaguch et al, have reported the reaction by using heterogeneous catalyst such as sulphated zirconia to overcome the difficulty in disposal of used catalyst in this reaction In this case, though the catalyst could be separated out after the reaction its regeneration for reuse was difficult Catalysts and Chemicals Aluminium chloride and benzene was obtained from S D Fine Chem Ltd 4-chlorobenzoyl chloride was obtained from Merck Ltd All the chemicals were analytical grade and were used without further purification Preparation of UDCaT-1 5g Dodecyl amine was dissolved in 41 8g of ethanol and 29 6g of distilled water 20 8g of tetraethyl orthosilicate was added under vigorous stirring to it The addition of ethanol improved the solubility of the template The reaction mixture was kept for aging for 18 hours at 30°C The clear liquid above the white coloured precipitate was decanted and the prcipitate HMS, was dried on a glass plate The template was removed either by calcining the resulting material at 550°C in air for 3h or by refluxmg the dried HMS material twice in 150 ml ethanol for 1h and drying it at 80°C in an oven for2h 2 5g Zirconium oxychlonde dissolved in 10ml of distilled water was added in drops to the 5g of calcined HMS with vigorous mixing special precaution was taken during the said procedure of adition aqueous solution of zirconium oxychlonde in calcined HMS After every little addition of the solution, the solid was partially dried over a boiling water bath Ultimately, after all the addition was over, the solids were dried in an oven at 120°C for 1h The dried material was loaded in a reactor and ammonia gas was passed through it for 3h The ammoniated sample was washed with distilled water to remove the chloride ions and dried in oven at 120°C for 2h The sulfation was done by passing 1N sulfuric acid (15ml/g) through the filter paper containing the dried ammoniated solid material It was then dried in an oven for 1h at 120°C and calcined at 550°C for 3h to give the active catalyst UDCaT-1 Expenmental setup The reactor consisted of a flat glass vessel of 5 cm i d , 10 cm height and 150ml of capacity equipped with baffles and a six blade impeller The assembly was kept in an oil bath at 65-70°C The reaction mixture could be agitated at the required speed with the help of a variable motor Reaction procedure 4-chloro benzoyl chloride ( 0 02 moles) and benzene ( 0 2 moles) were fed into the reactor Catalyst ( 0 02 moles ) was added to the reaction mixture and the reaction mixture was heated at reflux temperature An initial sample was then drawn and the agitation started The reaction was monitored by periodic withdrawal of samples The samples were analysed on HPLC (Model Toscho, UV-8010) by using C18 supported on silica column Mobile phase methanol water (60 40) were used for analysis of the samples The quantitative analysis was done by comparison with standard synthetic mixtures After 5 hrs, benzene was removed by distillation and reaction mixture were poured into water which contained dil hydrochloric acid to neutralise the mixture Results Conversion and yield are given in Table 1 Examples 2-10 Acylation of benzene with 4-chloro benzoyl chloride using catalysts other than aluminium chloride Catalysts and Chemicals Amberlyst-15 and Amberhte IR 120 were obtained from Rohm and Hass K-10 was a montmonllinite clay obtained from Fluka and Filtrol-24 clay was obtained from Engelhart Indion 130 was obtained from Ion Exchange (India) Ltd Dodecatungstophosphoric acid and benzene was obtained from M/S S D Fine chemicals Ltd Sulphated zirconia was prepared in our lab UDCaT-1 as described in Example 1 (See also co-pending Ind PAt Appin entitled "A process for preparation of a highly acidic mesoporous solid catalyst') 4-chlorobenzoyl chloride were obtained from Merck Ltd The catalysts used for the reaction were dried at 100°C under vacuum for 6 hr before use All the chemicals were analytical grade and were used without further purification Experimental setup The reactor consisted of a flat glass vessel of 5 cm i d , 10 cm height and 150ml of capacity equipped with baffles and a six blade impeller The assembly was kept in a oil bath at 65-70°C The reaction mixture could be agitated at the required speed with the help of a controllable motor Reaction procedure 4-chloro benzoyl chloride ( 0 02 moles) and benzene ( 0 2 moles) were fed into the reactor A catalyst (10% w/w) as shown in Table 1, was added to the reaction mixture and the reactor was heated to 70°C and maintained at 70 ± 1°C An initial sample was then withdrawn and the agitation started The reaction was monitored by periodic withdrawal of samples The samples were analysed on HPLC (Model Toscho, UV-8010) by using C18 supported on silica column A mobile phase methanol water (60 40) were used for analysis of the samples The quantitative analysis was done by comparison with standard synthetic mixtures After 4 hrs, when the reaction was complete and the product was isolated by distilling the excess quantity of benzene Results The conversion of 4-chlorobenzoyl chloride and the yields of the reaction in each of the examples using different catalysts are given in Table 1 Table 1 Acylation of benzene with 4-chlorobenzoyl chloride Activity of various catalysts (Table Removed) It will be seen that none of these catalysts of examples 2-8 were active for this reaction The catalyst of example 9 did not give yields better than that of AICI3 while example 10, using UDCaT-1 gave yield higher than the of AICI3 even though conversion was poor That shows less wastage It will be seen that the acylation reaction is very efficently carried out with UDCaT-1 catalyst Product were identified by IR spectra 1H NMR Melting point and purity also checked by HPLC method The repeated runs were carried out by decanting the original contents of the reactor and later adding fresh reactants into the reactor Care was taken that there was no loss of catalysts while the repeat experiments were carried out using the same used catalysts The results of these repeat experiments are given in Table 2 Table 2 Acylation of benzene with 4-Chlorobenzoyl chloride Repeat use of catalyst - UDCaT-1 (Table Removed) Examples 11-16 Alkylation of p-cresol with Methyl tert-butyl ether (MTBE) It is well known that apart from its being a fuel oxygenate, MTBE has been employed as an excellent alkylating agent whereby only methanol would be a byproduct of reaction Butylated hydroxy toluenes (BHT) are among the well known industrial antioxidants and the basic raw materials for the manufacture of oil-soluble phenol formaldehyde resins that are conventionally prepared by the alkylation of p-cresol with isobutylene BHT are the usual source of isobutylene is the C4 cut from the refineries On cracking, MTBE gives high purity isobutylene Further MTBE forms a homogeneous phase with p-cresol and thus monitoring the reaction becomes easier The alkylation of p-cresol with MTBE has been studied with UDCaT-1 and has been found to give good activity Catalysts Filtrol-24, K-10, lndion-130 and HPA/K-10 were used Filtrol-24 was obtained from Engelhardt K-10 was obtained from fluka lndion-130 used was a product of Ion Exchange (I) Ltd Chemicals p-Cresol was obtained from s d fine Chem(l) Ltd MTBE was obtained from Texas Petrochemicals, USA Other chemicals used were obtained from firms of repute Reaction procedure All experiments were carried out in a Parr Autoclave of 100 ml capacity equipped with a four blade pitched turbine impellar The temperature was maintained at + 0 5°C of the desired temperature The intrument was also equippped with a spped regulator that could maintain the speed at +5 rpm of the desired speed A predetermined quantity of reactants and the catalysts was charged into the autoclave and the temperature was raised to the desired value Once the temperature was attained the initial sample was withdrawn ahich was the zero time sample Further samples were drawn st periodic intervals A typical standard experiment contained 0 22 mole (19 61g) of MTBE, 0 22 moles (24 31 g) of p-cresol and 3 5% w/w catalyst, based on reaction mixture The temperature was maintained at 100°C and the speed of agitation was 700 rpm Analysis The samples were analysed on a gas chromatograph (Perkin Elmer Model 8500 ) equipped with a flame lonisation detector A 2m x 0 003m column was used The stationary phase was 10% OV-17 supported on chromosorb WHP The GC conditions were as follows Carrier gas Nitrogen Carrier Flow 20ml/min Inj temperature 300°C Det Temperature 300°C Oven conditions (Table Removed) The quantitative analysis was done by comparison with standard synthetic mixtures Results Table 3 gives the % conversion of p-Cresol and selectivity to BHT with different types of catalysts As from Table 3 UDCaT-1 is giving better conversion of p-cresol and selectively forming 2-tert-butyl-p-cresol Table 3 Activity of various catalysts for the alkylation of p-cresol with MTBE (Table Removed) Examples 17-22 Fnedel-Crafts alkylation benzene / toluene with benzyl chloride In these examples Friedel-Crafts alkylation of benzyl chloride with benzene and toluene were carried out with classical AICI3, different bi-transition metals and UDCaT-1 as catalyst Supported clays are the recent of the Friedel-Crafts alkylation catalysts reported to have exceptionally high activity for the reaction of benzyl chloride with benzene to give diphenylmethane Diphenyl methane & diphenyl toluene are useful drug & pesticide intermediates, the reaction which uses the conventional AICI3 as the catalysts has several pollution problems & the reaction proceeds vigorously and is dangerous Chemicals Aluminium chloride and ferric chloride were obtained from sd Fine Chem Ltd K-10 was obtained from Fluka Benzene, benzyl chloride and toluene were products of s d Fine Chem Ltd Catalysts A bitransitional metal halide constituting of ferric chloride and aluminium chloride, HPA supported on K-10 were prepared as per our Ind Pat Aluminium chlonde and ferric chloride supported in the ratios of 0 1, 1 3, 3 1, 1 0 were also prepared by the process described UDCaT-1 was prepared as des+cribed under Example 1 Experimental The reactor consisted of a flat glass vessel of 5 cm i d amd 10 cm height equipped with baffles and a six blade impeller located at a height of 0 5 cm from the bottom The assembly was kept in a water bath to maintain constant temperature The reaction mixture could be agitated at the required speed with the help of a variable motor Reaction procedure All experiments were carried out by charging 39 50 mmol of benzyl chloride and 197 mmol each of benzene and toluene into the reaction vessel Catalyst loading was 0 55gm The reaction was carried out at 45°C Under such conditions 100% conversion was observed in 40mm The reaction products are recovered by distillation The products were diphenylmethane and benzyltoluene The reaction was h.ghfy selective and no side products were formed Analysis Samples were analysed on a Chemito Gas Chromatography by using a lonisation detector and a spectrophysics integrator For the analysis a S S column 94x3 mm) packed with OV-17 on chromosorb was used The column conditions were maintained as follows The quanitative analysis was done by calibrating with synthetic mixtures Results Conversion and Selectivity were shown in Table 4 Table 4 Compantive activities of the supported catalysts (Table Removed) The results show that between these catalyst UDCaT-1 is only the ecofriendly catalyst that gives conversion and selectivity similar to other non-ecofnendly catalysts Examples 23-27 The invention will now be illustrated with the help of Examples The Examples are by way of illustration only and in no way restrict the scope of the invention Examples 23-27 Chemicals All chemicals were procured from firms of repute Tetraethyl orthosilicate (TEOS) (Fluka) was taken as the neutral silica source and dodecyl amine (Spectrochem Ltd) as the neutral amine surfactant for the templates Zirconium oxychlonde, ammonia solution (AR grade), ammonium sulfate (AR grade) aniline (AR grade) and ferf-butanol (AR grade) were procured from M/s, Loba Chemie and sd Fine Chemicals Ltd respectively Ethanol was purified by distillation and treatment with calcium oxide Catalysts SO42 - Zr02was prepared by the method given by Hino and Arata (Hino M Arata K J ChemSoc, Chem Commun, 24, (1980), 851-852) HMS and UDCaT-1 were prepared as follows Preparation of UDCaT-1 The hexagonal mesoporous silicate (HMS) was prepared with following procedure 5g dodecyl amine was dissolved in 41 8g of ethanol and 29 6g of distilled water 20 8g of tetraethyl orthosilicate was added under vigorous stirring to it The addition of ethanol improve the solubility of the template The reaction mixture was aged for 18 hours at 30°C The clear liquid above the white coloured precipitate was decanted and the prepitate HMS, was dried on a glass plate The template was removed either by calcining the resulting material at 550°C in air for 3h or by reflexing the dried HMS material twice in 150 ml ethanol for 1h and drying it at 80°C in an oven for 2h 2 5g zirconium oxychlonde dissolved in 10ml of distilled water was added in drops to the 5g of calcined HMS with vigorous mixing Special pecaution was taken during the said procedure of addition aqueous solution of zirconium oxychlonde in calcined HMS After very little addition of the solution, the solid was partially dried over a boiling water bath Ultimately after all the addition was over, the sohdes were dried in an oven at 120°C for 1h The dried material was loaded in a reactor and ammonia gas was passed through it for 3h The ammoniated sample was washed with distilled water to remove the chloride ions and dried in oven at 120°C for 2h The sulfation was done by passing 1N sufuric acid (15 ml/g) through the filter paper containing the dried ammoniated solid material It was dried in oven forlh at 120°C and calcined at 550°C for 3h to give the active catalyst UDCaT-1 Reaction Procedure The tert-butylation of aniline was carried out in a vapour phase fixed bed catalytic reactor at atmospheric pressure 1 0 g of catalyst sample was placed in a tubular down flow glass reactor (40 cm x 1 5 cm) and the catalyst section was packed between two sections of glass wool The reactants mixed in a proper ratio were fed from the top by using a calibrated motonsed syringe pump Glass beads loaded at the top of the catalyst bed were used as pre-heating zone Nitrogen was used as the carrier gas and the flow rate was controlled by a rotameter at a range of 15 ml/mm and 30 ml/mm It was calibrated carefully with a soap film meter in every run Examples 35-39 were carried out using different catalyst at feed rates and temperature region as given below in the Table 2 The liquid products were obtained by circulating cold water through the condenser Aniline was separated by distillation and the product 4-ferf-butylanihne was obtained In example 39 a run of 3 hrs gave 10 g of aniline and 4-tert-butylaniline mixture On distillation it gave 2 5 g of 4-fe/t-butylanihne Analysis of Reaction Mixture The products were analysed by gas chromatography (Model Chemito 8510) using 4 m x 3 mm i d stainless steel column packed either with 5 % SE -30 or OV - 17 on chromosorb WHP, coupled with a flame lonisation detector Synthetic mixtures of reactants and products were used to calibrate the G C results for quantification A typical mass spectral fragmentation pattern of alkylated product proves that the product obtained is mono alkylated product The 1H NMR (500 MHz) spectra shows that the product formed is 4-terf-butyl aniline The mass spectral fragmentation pattern of aniline alkylation reaction mixture confirming the mono alkylation The separated product was then further analysed by 1H NMR for its mono alkylation 1H NMR (500 MHz) using CDCI3 δ 7 25 (d J= 8 514 Hz, 2H), δ 6 7 (d, J=8 483, 2H), δ 3 78 (s, 2H), δ 1 35 (s, 9H) spectra shows that the product formed is 4-terf-butyl aniline Thus N- alkylation was totally absent using UDCaT-1 whereas it was a major product in the case of DTP/ K-10 as a catalyst as reported elsewhere (Doshi NS, PhD Thesis, University of Mumbai 1998) The reaction results are summarised in Table 2 Results Table 10 gives the % conversion of aniline and selectivity to 4-terf-butyl aniline with different types of catalysts As from Table 5 UDCaT-1 is giving better conversion of aniline and selectivity forming 4 - tert - butyl aniline Table 5 Alkylation of aniline with tert-butanol (Table Removed) Reaction Conditions =Anilline and tert-butanol were taken in 1 4 mole ratio, Catalyst loading = 1 g , Reaction temperature = 250 °C Reactant feed rate = 65 ml/ h a Nitrogen flow rate = 30 ml/ mm b Nitrogen flow rate = 15 ml/ mm c 4-tert- butylaniline Examples 4 and 5 show high conversion and high selectivity In continuous processes the isobutylene vapours can be recirculated and yields should be high. WE CLAIMS :- 1. A process for vapour phase alkylation reaction for selectively forming monoalkylated arylamine, alkylated at para-position, products comprising : i) contacting arylamines with alkylating agent both in vapour phase in presence of highly acidic mesoporous solid catalyst (UDCaT-1) such as herein described ; ii) maintaining the reaction temperature between 150 - 400°C in the tubular flow reactor; iii) recovering the reaction product by conventional methods. 2. A process as claimed in claim 1 wherein said arylamine is selected from the group comprising, aniline, alkylated anilines, halogenated anilines, hydroxylated anilines. 3. A process as claimed in claims 1 or 2 wherein said alkylating agent is selected from a group comprising alkanols with carbon number from C2 to C16, cylic alcohols such as cyclohexanol and olefins such as ethylene, propylenes, butylenes, isoarmylene, cyclohexene, and other a-olefines. 4. A process as claimed in anyone of claims 1 to 3 wherein the catalyst used in sulfated metal oxide molecular sieve catalyst having synergistic combination of sulfated metal oxide and mesoporous zeotypes having surface area of 200-500 m2/g pore volume of 0.1 to 0.3 m3/g pore diameter of 25-35°A 5. A process as claimed in claims 1 to 4 wherein said catalyst used comprised XRD(20) of 0-3° and elemental Si in an amount of 50-60% by wt. S in an amount of 5-10% by wt. And Zr in an amount of 40-50% by wt. 6. A process as claimed in claims 1 to 5 wherein arylamine is aniline and alkylating agent is ferf-butanol. 7. A process as claimed in claims 1 to 6 wherein the ratio of the arylamine to alkylating agent is between 4:1 to 1:10. 8. A process for vapour phase alkylation reaction substantially as herein described and illustrated with reference to the accompanying examples.

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