Abstract:
N-alkylated anilines can be prepared by reaction of anilines with lower alcohols or dialkyl ethers at elevated temperature and in the presence of zeolite catalysts of the pentasil type containing protons and having an SiO 2  /Al 2  O 3  ratio of at least 60.

Description:
BACKGROUND OF THE INVENTION 
     The present invention relates to a process for the preparation of N-alkylated anilines by reaction of anilines with lower alcohols or dialkyl ethers at elevated temperature and in the presence of proton-containing zeolites of the pentasil type having an SiO 2  /Al 2  O 3  ratio of at least 60. 
     N-alkylated anilines are important industrial intermediates for the preparation of dyestuffs, stabilizers, urethanes, ureas, pharmaceuticals and plant-protection agents. They are usually prepared by alkylation of anilines with alcohols in the presence of acidic catalysts, for example phosphorus oxychloride, under pressure or by passing aniline and alcohol vapors together through hot phosphoric acid at atmospheric pressure. 
     These processes are unsatisfactory in some respects. The reaction in an autoclave under pressure is industrially expensive, and the homogeneously dissolved acidic catalysts cause extensive corrosion. The phosphoric acid process at atmospheric pressure has this disadvantage to a lesser extent, the relatively large amount of phosphoric acid becomes unusable as a catalyst over time and has to be disposed of and replaced by fresh phosphoric acid. 
     It is true of both processes that they have only relatively little flexibility with respect to the alternating preparation of N-monoalkylanilines and N,N-dialkylanilines. 
     Zeolites have already been proposed as catalysts for these reactions, and it has been shown that both N-monoalkyl- and also N,N-dialkylanilines can be obtained. However, other disadvantages arise. 
     According to Waseda Daigaku Rikogaku Konkyusho Hokoku 69 (1975), 21-25 (cited in C.A. 84 (1976), 121 339 k), Y-zeolites and also H-Y as well as those exchanged with Cu, Ni, Co, Mn, Zn, Ca and Ce ions are suitable as catalysts for the reaction of methanol with aniline to give N-methylated anilines. However, from Table 1 on page 23 of this reference, it can be seen that all reactions are accompanied by the formation of toluidine, that is, by ring-alkylation. The highest activity (100 % of conversion) and one of the highest rates (86%) of N-methylation is shown by H-Y, however only at an uneconomical molar ratio of methanol: aniline=3:1. The highest N-methylation rate (92 %) is shown by Cu-Y, in which case, however, the conversion is significantly less (44.9%) and the formation of toluidine is still 3.4%. 
     In addition, the reaction on Cu-Y and H-Y has a very unfavorable temperature dependence, since a useful conversion is achieved only in a very narrow temperature range around 250° C. (cf. FIGS. 1 and 2 on page 22), whereas at other only slightly changed temperatures not only conversion but also yield in N-alkylated anilines decrease. 
     P. Y. Chen, M. C. Chen, H. Y. Chu, N. S. Chang and T. K. Chuang, Proc. 7th Intern. Zeolite Conf. Y. Murakami, A. Iijima and J. W Ward (Eds.), p. 739-744, Kodansha, Tokyo and Elsevier, Amsterdam, Oxford, New York, Tokyo 1986 show in their investigation of N-methylation of aniline with methanol on ZSM-5 zeolites that ring-alkylation is always observed and they are convinced that it is caused by active centers on the surface of the zeolites. Furthermore, not only the basic but also the acidic properties of the zeolites are said to have been responsible for catalytic activity in such a manner that upon impregnation of the zeolites with metal oxides ring-alkylation decreases. Yet, even under the most favorable conditions (table on p. 744) using MgO/H-ZSM 5, noticeable ring-alkylation is still found. In addition, a temperature of 350° C. and a large excess of methanol must be used. This indicates a very low activity of these zeolites. Furthermore, an increase in SiO 2  /Al 2  O 3  ratio results in decreasing conversion of aniline (FIG. 1 on p. 741). Admittedly, the selectivity increases but even in the most favorable case ring-alkylation still amounts to several % (FIG. 2 on p. 742). Consequently, the acidic H-ZSM 5 appears to be the least suitable zeolite. It almost produces the lowest aniline conversion and is rapidly deactivated (FIG. 3 on p. 743) and furthermore causes one of the highest ring-alkylation rates (Table 2 on p. 743). 
     SUMMARY OF THE INVENTION 
     Surprisingly it has now been found that protoncontaining zeolites of the pentasil type having an SiO 2  /Al 2  O 3  ratio of at least 60 represent significantly better catalysts for the N-alkylation of anilines with alcohols, cause only minor or practically no ring-alkylation, have improved service lives and accomplish good conversions even at a low alcohol/aniline ratio. 
     Accordingly, the invention relates to a process for the preparation of N-alkylated anilines of the formula ##STR1## by reaction of anilines of the formula ##STR2## in which formulae 
     R 1  denotes C 1  -C 4  -alkyl and 
     R 2  denotes hydrogen or C 1  -C 4  -alkyl and 
     R 3  and R 4  independently of one another stand for hydrogen, C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, fluorine, chlorine or bromine with C 1  -C 4  -alcohols or the corresponding dialkyl ethers in the presence of zeolites at elevated temperature, which is characterized in that the zeolites used are those of the pentasil type containing protons and having an SiO 2  /Al 2  O 3   ratio of at least 60. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Suitable anilines for the process according to the invention are those of the formula (II), for example aniline or the isomeric toluidines, fluoroanilines, chloroanilines, bromoanilines, xylidenes, ethylanilines, isopropylanilines and others which result from (II). Preference is given to those anilines in which R 11  =C 1  -C 2  -alkyl alkyl and R 12  =hydrogen or C 1  -C 2  -alkyl take the place of R 1  and R 2 . Further preferred anilines are those in which R 13  and R 14  independently of one another denoting hydrogen, C 1  -C 2  -alkyl, C 1  -C 2  -alkoxy, fluorine or chlorine, preferably R 23  and R 24  denoting independently of one another hydrogen, C 1  -C 2  -alkyl or chlorine, take the place of R 3  and R 4 . 
     Examples of alkylating agents suitable for the process according to the invention are dimethyl ether, diethyl ether, methanol, ethanol, propanol, isopropanol, butanol or isobutanol, preferably methanol and ethanol. 
     The reactants can be diluted by inert gases such as nitrogen or water vapor or by inert solvents such as hydrocarbons, for example pentane, cyclohexane, methylcyclohexane, isooctane, benzene, toluene, xylene, cumene or ethylbenzene. 
     Suitable zeolites for the process according to the invention are pentasils containing protons and belonging to the formula 
     
         H(M.sub.m/z)[mAlO.sub.2 ·nSiO.sub.2 ]·qH.sub.2 O (III) 
    
     in which 
     n/m, calculated as the SiO 2  /Al 2  O 3  ratio, is at least 60, 
     (M m/z ) represents the metal cations present in the pentasil as replacement for some of the hydrogen ions, 
     z indicates the valence of these cations and 
     q indicates the amount of water phase adsorbed. 
     The SiO 2  /Al 2  O 3  ratio is, for example, 60 to 2,000, preferably 70 to 1,500, particularly preferably 80 to 1,000. 
     Examples of preferred pentasils are ZSM 5, ZSM 11, ZSM 8, ZSM 5/ZSM 11-intermediates, zeta 1, zeta 3, ZBM 10, ultrasil, ultrazet, TZ-01, NU-4, NU-5 and AZ-1. Pentasils of the type ZSM 5, ZSM 8, ZSM 11 and ZSM 5/ZSM 11-intermediates are particularly preferred. Pentasils of the ZSM 5 type are very particularly preferred. The preparation of these pentasil types is known. Reference can be made to D. W. Breck: Zeolite Molecular Sieves, John Wiley and Sons Inc., New York 1974, Russ. J. Phys. Chem. 55 (1981), 1175 and European Patents 18,090, 34,727, 54,386, 57,016, 65,401, 113,116, DE-OS (German Published Specification 2,548,697, DE-OS (German Published Specification) 2,643,929, U.S. Pat. No. 3,702,886, U.S. Pat. No. 3,709,979 and GB Patent 1,334,243. 
     The pentasil zeolites suitable for the process according to the invention can contain exclusively protons as the cations. However, up to 80 equivalent % of the protons can also be substituted by other ions. The ions suitable for this purpose are, for example, those of sodium, potassium, magnesium, zinc, cobalt, copper, calcium, iron, the rare earths (for example cerium, lanthanum), tin, manganese, chromium, titanium, zirconium, tantalum and others. Preferably, a maximum of 50 equivalent %, particularly preferably a maximum of 25 equivalent %, very particularly preferably a maximum of 10 equivalent % and most preferably a maximum of 5 equivalent %, of the protons are substituted in the pentasils by others of the metal cations mentioned. 
     The reaction of the process according to the invention can be carried out batchwise with stirring in liquid phase and under the resulting pressure, it being possible for the pentasil zeolites to be used in compact or in powdered form. The amount of pentasil is 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 7 to 30% by weight, relative to the total weight of the batch. 
     Furthermore, the reaction can be carried out continuously in the gas phase. ln this type of operation, the reaction can be in particular carried out at atmospheric pressure. Such a continuous operation is preferred for industrial application. For this purpose, an aniline/alcohol vapor mixture which is undiluted or diluted with inert gas or inert vapor is passed over a catalyst bed of penlasil zeolite present in grain form. The space velocity can in this case be varied within wide limits. Good conversions are obtained by adjusting the space velocity in the range from 0.01 to 8.0, preferably 0.05 to 5.0, particularly preferably 0.1 to 4.0 liters, of mixture to be reacted liter of catalyst/hour. 
     To convert the pentasil zeolites into a compact form, which is favorable for the operation of a gas phase reactor, they are compacted with binders and granulated. Suitable binders are various clays, aluminosilicates and aluminum oxides, in particular γ-Al 2  O 3  and SiO 2 . These binders are used in amounts of 15 to 50% by weight, relative to the ready-to-use zeolite catalysts. 
     The reaction temperature is 220° to 370° C., preferably 240° to 350° C., particularly preferably 260° to 330° C. 
     The ratio of aniline to alcohol is largely variable. However, it also determines which ratio of N-mono-alkylated to N,N-dialkylated anilines are obtained in the reaction product. Thus, an amount of 0.5 to 3 roles of alcohol/mole of aniline can in general be used, preferably 0.7 to 2 moles. If a high percentage of N-monoalkylated aniline is desired, the reaction should be carried out at a molar ratio alcohol: aniline of 0.5:1.2, preferably 0.7:1.0. 
     EXAMPLE 1 
     10 moles each of aniline and methanol were dissolved in 1.5 ml of benzene and, after the addition of 0.25 g of one of the zeolites mentioned, the mixture was heated at 300° C. for 3 hours. Table I below contains more detailed data of the individual experiments and the results obtained. 
     Examples 1.1 to 1.5 are according to the invention and show high selectivities of N-methylation at a high aniline conversion. Depending on the molar ratios of aniline/methanol, high selectivities of N-monomethylation (1.1, 1.2, 1.4) or N,N-dimethylation (1.3) could be obtained. Comparative Examples 1.6 and 1.7 have high ringalkylation rates under the same conditions. 
     EXAMPLE 2 
     A reaction tube, about 20 mm in diameter, was charged with 20 g of zeolite granules having an average particle size of 1 to 2 mm. A mixture of aniline and methanol vapor was passed over these zeolite granules at different space velocities and different temperatures for several hours. Exact conditions and results of these experiments are listed in Table II. According to Examples 2.1 and 2.2, selective N-methylation could also be obtained in the gas phase reaction at atmospheric pressure. Even after 35 hours of operation, no change in the activity of the H-ZSM 5 zeolite took place in Example 2.3. Even at an extremely high SiO 2  /Al 2  O 3  ratio, a high selectivity with respect to N-alkylation (Example 2.4) was still obtained. A higher supply of aniline significantly improved the selectivity with respect to N-monoalkylation (Example 2.5), which gave evidence of the flexibility of the process according to the invention. It is true that Comparative Example 2.6 under comparable conditions using a non-acidic Na-ZSM 5 gave a good selectivity of N-methylation, but it gave only a completely inadequate conversion. It is true that at higher temperatures it was possible to increase the conversion according to the abovementioned prior art, but at the same time the percentage of ring-alkylation was also increased. 
     
                                           TABLE I__________________________________________________________________________                  Product Distribution          Molar ratio                  in % by weightNo.   Catalyst    SiO.sub.2 /Al.sub.2 O.sub.3          Aniline/MeOH                  A NMA NNDMA                             ring-alk A__________________________________________________________________________1.1   H-ZSM 5    100   1:1     15                    62  23   &lt;0.31.2   Sn-ZSM 5    100   1:1     26                    55  19   &lt;0.31.3   H-ZSM 5    100   1:7     0.5                     5  93   1.81.4   H-ZSM 5    100   0.5:1   54                    40   6   &lt;0.11.5   H-ZSM 11    110   1:1     33                    49  17   &lt;11.6   H-Y   4.9   1:7     2.8                     1  65   301.7   Ca-Y  4.8   1:1     28                    42  18   12__________________________________________________________________________ A = Aniline NAM = Monomethylaniline NNDMA = N,Ndimethylaniline MeOH = Methanol 
    
     
                                           TABLE II__________________________________________________________________________              Molar     Space                             Time on                                  Product distribution              ratio Temp.                        velocity                             stream                                  in % by weightNo.   Catalyst  SiO.sub.2 /Al.sub.2 O.sub.3              A/MeOH                    °C.                        ml/ml/h                             h    A NMA NNDMA                                             ring-alk__________________________________________________________________________                                             A2.1   H-ZSM 5 + 30%        107   1:1   300 0.5  5    30                                    40  29   &lt;0.4   γ-Al.sub.2 O.sub.32.2   H-ZSM 5 + 30%        107   1:1   280 0.5  5    40                                    36  24   &lt;0.1   γ-Al.sub.2 O.sub.32.3   H-ZSM 5 + 15%        107   1:1   290 0.6  35   46                                    34  10   0   SiO.sub.22.4   H-ZSM 5 + 30%        800   1:1   300 1.0  4    48                                    32  19   &lt;1   γ-Al.sub.2 O.sub.32.5   H-ZSM 5 + 30%        107   2:1   300 1.0  7    60                                    31   9   0   γ-Al.sub.3 O.sub.32.6   Na-ZSM 5 + 30%        107   1:1   300 1.0  3    85                                    10   5   &lt;0.3   γ -Al.sub.2 O.sub.3__________________________________________________________________________ 
    
     EXAMPLE 3 
     The procedure as described in Example 2 was repeated. However, the alkylating agent used was ethanol and it was used in a molar ratio of aniline:ethanol=1:1. All reactions were carried out at 300° C. and at a space velocity of the catalyst of 1.0 ml/ml/h (see Table III). 
     Using ethanol also gave a high selectivity in N-alkylation (3.1 and 3.2). N-monoalkylation under the same conditions turned out to be higher in this case than in the N-methylation. The Y-aluminum oxide by itself, which was used as binder material, has under the reaction conditions too little conversion, ring-alkylation and rapid deactivation (Comparative Example 3.3). 
     EXAMPLE 4 
     Under the conditions of Example 3, m-toluidine was reacted with ethanol. 
     Using H-ZSM 5, the expected virtually 100% N-alkylation and no reduction in catalyst activity after 100 hours were found (4.1). 
     In Comparative Example 4.2 using H-Y, a considerable percentage of m-toluidine was, as already shown in Example 1.5, alkylated on the ring. 
     
                                           TABLE III__________________________________________________________________________                   Product distribution in %              Time on                   by weightNo.   Catalyst  SiO.sub.2 /Al.sub.2 O.sub.3              stream                   A NEA NNDEA                              ring-alkyl.A__________________________________________________________________________3.1   H-ZSM 5 + 15% of        107   4    48                     48  4    0.1   SiO.sub.23.2   H-ZSM 5 + 30% of        107   4    41                     52  6    &lt;1.5   γ-Al.sub.2 O.sub.33.3   γ-Al.sub.2 O.sub.3        --    4    77                     20  --   3 (rapid deactivation)__________________________________________________________________________ NEA = Nethylaniline NNDEA = N,Ndiethylaniline 
    
     
                                           TABLE IV__________________________________________________________________________              Time on                   Space                        Product distribution in %              stream                   velocity                        by weightNo.   Catalyst  SiO.sub.2 /Al.sub.2 O.sub.3              h    ml/ml/h                        mT NET                              NNDET                                   ring-alkyl.T__________________________________________________________________________4.1   H-ZSM 5 + 30% of        107   100  1.3  43 52 5    &lt;0.1   γ-Al.sub.2 O.sub.34.2   H-Y + 30% of        4.6   4    1.0  34 50 6    10   γ-Al.sub.2 O.sub.3__________________________________________________________________________ mT = mtoluidine NET = Nethyl-m-toluidine NNDET = N,Ndiethyl-m-toluidine