Formation of ortho-alkylated aromatic amines from N-alkylated aromatic amines

TECHNICAL FIELD
This invention pertains to a process for the conversion of N-alkylated aromatic amines to the ortho-alkylated counterpart.
BACKGROUND OF THE INVENTION
Processes for alkylating a variety of aromatic compounds by contacting such compounds with a hydrocarbon radical providing source such as an olefin or alcohol with an alkylatable aromatic compound are widely known. Typically, alkylatable aromatic compounds have included mononuclear aromatic compounds themselves or aromatic compounds containing polar substituents such as a hydroxyl, an amino, an alkoxy, a halogen group and so forth. The catalysts utilized in the alkylation reactions have been acidic; e.g., Lewis acids and used as Friedel-Crafts catalyst systems.
To facilitate an understanding of the scope of alkylation of aromatic compounds including the types of aromatic compounds which are alkylatable and the catalyst systems, reference is made to the following patents:
U.S. Pat. No. 2,115,884 discloses the alkylation of aromatic hydrocarbons such as benzene and napthalene, as well as their halogen, nitro, carboxylic acid, and amine derivatives. The alkylation is effected by contacting the aromatic compound with an olefin while using a hydrated silica or bleaching earth as a catalyst. Temperatures of about 140.degree.-260.degree. C. are used.
U.S. Pat. Nos. 3,733,365; 2,923,745; and 3,701,811 disclose the alkylation of hydroxy aromatics, e.g. phenol, by contacting the aromatic compound with an olefin or alcohol. The catalyst systems utilized in these alkylation processes include polymeric aluminum alcoholates, active alumina activated with an aluminum alcoholate, aluminum halides and metal oxides such as cerium oxide or uranium oxide disposed upon inert carriers such as gamma-alumina, silicon carbide, silica and natural clays, molecular sieves and alumino-silicates.
The ring-alkylation of aromatic amines has generated considerable interest because the aromatic monoamines are valuable intermediates in the manufacture of herbicides, dyestuffs, auxiliaries for rubber and plastics and for textiles. Alkylated diamines have many of the same uses that the mono aromatic amines have, but they may also be used as cross linkers for producing a variety of polyurethanes. The alkylated aromatic amines, particularly toluenediamine, when alkylated have a lower reactivity than the parent aromatic amine and this permits manufacturers to form a variety of molded products in a way that could not be formed earlier. Reaction injection molding (RIM) is one of these processes which lends itself to the use of ring-alkylated aromatic diamines as chain extenders for polyurethanes.
Early processes for the ring-alkylation of aromatic amines resulted from the reaction of aniline hydrochloride with alcohols. Similar results were obtained when an N-alkylanilinium halide was heated and caused to rearrange to the ring alkylated product. This work was done by Hofmann and Martius.
Reilly and Hickenbottom, published in a series of articles, one appearing in J. Chem. Soc., 117, 103, (1920) that nuclear alkylation of amines could be effected by heating an N-alkylaniline with a Lewis acid, such as, zinc chloride.
U.S. Pat. Nos. 3,649,693; and 3,923,892 disclose the preparation of ring-alkylated aromatic amines where the alkyl group is ortho to the amine. The U.S. Pat. No. '693 discloses ring alkylation by reacting an aromatic amine with an olefin in the presence of aluminum anilide. The U.S. Pat. No. '892 shows the alkylation in the presence of an alkyl aluminum halide such as diethyl aluminum chloride. The U.S. Pat. No. '892 shows the alkylation reaction in the presence of aluminum anilide.
Stroh et al in U.S. Pat. No. 3,275,690; 2,762,845; West German AS No. 1,051,271 and Japanese No. 38-4569 disclose various processes for the manufacture of alkylated aromatic amines by effecting reaction between an aromatic amine and an olefin. Representative aromatic amines for alkylation include primary amines, such as, aniline, toluidines, xylidines; secondary amines such as diphenylamine and diamines such as m-phenylenediamine and various toluenediamine isomers. In the U.S. Pat. No. '690, various Friedel-Crafts catalysts such as aluminum chloride, zinc chloride, boron fluoride and other halogen compounds are combined with aluminum to effect the catalytic reaction. In the U.S. Pat. No. '845, aluminum powder is used as a component of the catalyst system. The West German No. '271 uses various bleaching earths and montmorillonite as the catalyst.
Most of the above processes utilize homogeneous catalysis. However, the heterogeneous catalysis of the alkylation of aromatic amines is shown in U.S. Pat. No. 2,115,884; British patent No. 846,226; U.S. Pat. Nos. 4,351,958 and 4,446,329. The U.S. Pat. No. '884 discloses the ring alkylation of aromatic hydrocarbons using activated hydrosilicates and hydrated silicic acids, commonly referred to as bleaching earth. The U.S. Pat. No. '958 discloses the use of iron oxide as a catalyst for such alkylation and the U.S. Pat. No. '329 discloses the use of a metal cation salt of a perfluorosulfonic acid polymer, the polymer typically being sold under the trademark Nafion.
Japanese Patent No. 59-167545 discloses the reaction of N-isopropyl-3-methylaniline in the presence of propylene and a Friedel-Crafts catalyst. The 3-methyl-4-isopropylaniline derivative is produced.
One of the problems associated with the ring-alkylation of aromatic amines with an olefin, even though such processes are alleged to be effective for ortho-alkylation or para-alkylation, is that a large amount of N-alkylated aromatic amine is produced. The N-alkylated product formed in amounts from 2-45% by weight of reactant must be converted to a ring-alkylated product in order for the overall process to have any industrial success. A second problem associated with the ring-alkylation of N-alkylated aromatic amines is that the N-alkylated aromatic amine readily rearranges in the presence of the catalyst to the para-isomer. Under alkylation conditions, particularly at high conversions, e.g., greater than 20%, the amount of para-isomer formed is quite high in relation to the amount of ortho-isomer. Typically, the ortho-para isomer ratio is less than 3:1 and generally less than 1:1. Some other problems described herein regarding the synthesis of ortho-alkylated amine products and those problems associated with the production of N-alkylated aromatic amines are well-illustrated in U.S. Pat. No. 4,351,958, Column 1, lines 32-67, and Column 2, lines 1-34.
SUMMARY OF THE INVENTION
This invention pertains to a process for enhancing the conversion of N-alkylated aromatic amines to a ring-alkylated amine where the alkyl group is ortho to the amine. Both high selectivity to the ortho-isomer as opposed to the para-isomer and high conversion to the ring-alkylated product is achieved. More particularly, the process for producing a reaction product having a high ortho to para isomer ratio of ring-alkylated product e.g. greater than 3:1 at greater than 20% conversion is effected by reacting a feed composition capable of alkylation in the ortho and para positions represented by the formula: ##STR1## where R is hydrogen or C.sub.1 to C.sub.10, X is 0, 1 or 2, R.sub.1 is C.sub.2 to C.sub.10 alkyl and R.sub.2 is hydrogen or C.sub.1 to C.sub.10 alkyl. The reaction is carried out by contacting the N-alkylated reactant with an olefin over a solid phase, acid catalyst, and maintaining an olefin to N-alkylate molar ratio of at least 1:1. The temperature employed in the reaction is that temperature which is sufficient to effect conversion of the N-alkylated reactant to ring alkylated product, but insufficient to effect substantial decomposition of the ortho-alkylated product as it is produced. During such reaction the pressure sufficient to aid in rearrangement is greater than 50 psig but not in excess of 3000 psig.
There are many advantages associated with this invention, and these include:
an ability to selectively generate ring-alkylated aromatic amines where the alkyl group is ortho to the amine as opposed to para to the amine; e.g., ratios greater than 3:1;
an ability to effect the catalytic reaction in the presence of a heterogeneous catalytic system which provides a mechanism for easy
separation of the catalyst from the reaction medium and a mechanism for continuous operation;
an ability to convert byproduct N-alkylated aromatic amine to valuable ring-alkylated product at high conversion; and
an ability to achieve ring-alkylation of N-alkyl aromatic amines at modest pressures, thus reducing capital costs with respect to equipment, while at the same time obtaining high reaction rates and conversions.

DETAILED DESCRIPTION OF THE INVENTION
The feedstock suited for practicing this invention contains an N-alkylated aromatic amine such as an N-monoalkyl aromatic amine or an N,N-dialkyl aromatic amine. Such N-alkylated aromatic amines typically result as a byproduct from the alkylation of aromatic amines such as aniline and toluidine. Such N-alkylated reactant is represented by the formula: ##STR2## where R is hydrogen or C.sub.1 to C.sub.10, X is 0, 1 or 2, R.sub.1 is C.sub.2 -C.sub.10 alkyl and R.sub.2 is hydrogen or C.sub.1 to C.sub.10 alkyl. Specific examples of N-alkylated reactants include N-ethylaniline, N-isopropylaniline, N,N-diethylaniline, N,N-diisopropylaniline, N-ethyl-2-toluidine, N-ethyl-2,4-xylidine, N-tert-butyl-2,4-xylidine, N-tert-butylaniline and the like. These amines may also be substituted with substituents inert to the alkylation reactions; e.g. halogen atoms; e.g., chloro and bromo; ester groups etc. Preferably R' is hydrogen or C.sub.1-4.
The alkylation of the N-alkylated reactant is achieved by reacting a C.sub.2 -C.sub.10, preferably C.sub.2-6, unsaturated olefin with the alkylatable aromatic amine reactant with the olefin to amine molar ratio being at least 1:1 and generally 2-10:1. Although other hydrocarbons have been utilized in the alkylation of aromatic hydrocarbons; e.g., alcohols, many of these alkylating agents undergo condensation with the N-alkylated reactant producing water which tends to destroy activity and alter the reactivity and selectivity to the ortho-isomer. Examples of olefins suited for practicing the invention include ethylene, propylene, isobutylene, pentene, and cyclohexene.
The catalysts used in the reaction of the present invention are those which are solid phase and which have sufficient catalytic activity to effect ring-alkylation. These catalysts must be acidic, although the degree of acidity of the catalysts may vary from one catalyst system to another. The only criteria is that the catalyst selected is sufficiently reactive for the aromatic compound and olefin selected to effect rearrangement. Examples of solid phase catalyst systems which are sufficiently active for effecting ring-alkylation of the N-alkylated aromatic amine include acidic zeolites, primarily those zeolites which have a pore size from 6 to 15 Angstroms and which have been ion exchanged with hydrogen or an acidic metal, e.g., lanthanum or other rare earth metal. Examples of such zeolite catalysts include mordenite, the Y and X faujasites, erionite, clinoptilolite the ZSM family and so forth. The zeolite also can be altered by the technique of "dealumination"; i.e., a technique where the alumina content is decreased in the zeolite. Dealumination, i.e., the removal of alumina from a zeolite structure has the effect of increasing the acidity of the catalyst system and also one of enlarging the pore size of the zeolite. Dealumination can be effected by acid treatment, chelation, dehydration, or steam treatment of the zeolite. A Si to Al ratio of a dealuminated zeolite typically will range from about 5 to 25:1.
These zeolites can be exchanged with various ions, preferably hydrogen or with a rare earth metal ion such as lanthanum, praeseodymium, and the like. The use of various ions in the structure will alter the acidity of the catalyst and therefore the reactivity in the alkylation reaction. Alkali metal ions create a zeolite catalyst which is less acidic and high temperatures may be required to effect alkylation. These high temperatures may influence transalkylation and thus formation of the para isomer. It should be recognized by those familiar with the utilization of zeolites in the alkylation of aromatic compounds that the pore size will vary between zeolites, and appropriately sized zeolites must be used to accommodate the synthesis of the higher molecular weight ring-alkylated aromatic amines and the multi-alkylated aromatic amine compounds. In most cases for alkylation, the pore size of the zeolite should be in excess of 7 Angstroms.
Other heterogeneous solid phase catalyst systems include montmorillonite, gamma-alumina, silica-alumina, and the like. Gamma-alumina is particularly effective for achieving high selectivity to ortho alkylated product.
The alkylation of N-alkylated aromatic amine is carried out at a temperature ranging from about 50.degree. to 375.degree. C. and typically at a pressure from about 50 to 3000 psig, typically 200-2000 and preferably from about 500-1000 psig. The temperature is controlled within this range at a temperature which is sufficiently high for the reactants to be reactive in the presence of the catalyst. Temperature control is an important variable in producing a reaction product which has a high ortho to para molar ratio and with a high conversion of N-alkylate to ring-alkylated product.
The alkylation of N-alkyl aromatic amine occurs with increasing ease as substitution of the double bond increases. For example, isobutylene will react faster than propylene and propylene will react faster than ethylene. Thus, an N-ethyl alkylated product will be stable at a higher temperature in the reaction zone than the N-isopropyl radical or the N-t-butyl radical under a given set of reaction conditions. Depending upon the acidity of the catalyst and activity of the amine, ethylene alkylation of N-ethylated aromatic amines may be accomplished at a temperature from about 200.degree.-425.degree. C., while the propylene alkylation may be effected within a range of 100.degree.-375.degree. C. and the isobutylene alkylation of N-t-butyl aromatic amine may be effected at a lower temperature; e.g., from 50.degree.-250.degree. C.
Temperature is an important parameter in achieving high conversion of the N-alkylated reactant to ring-alkylated product. However, as the temperature is increased for a given set of reaction conditions, there is the danger of effecting rereaction of the ortho-ring-alkylated product to form the para isomer or dealkylation of the ring-alkylated product. Typically, for ethylene alkylation of N-ethyl aromatic amine, the temperature should not exceed 425.degree. C. For propylene alkylation, the temperature should not exceed 375.degree. C. and for isobutylene alkylation, the temperature should not exceed 250.degree. C.
Reaction time is also an important factor in achieving high selectivity to the ortho-alkylated product at high conversion. Broadly, the reaction time can be expressed as a liquid hourly space velocity of feed components to the reactor and such expression will generate an LHSV of from 0.05 to 4 hours.sup.-1 and usually from 0.1 to 1 hr.sup.-1. If one is operating at relatively high temperatures for the alkylation reaction, the LHSV should be increased somewhat as longer reaction times permit increased formation of the para isomer. In those cases where high temperatures and long residence times are used, the rate of formation of ortho-isomer is less than the rate of dealkylation and transalkylation to para-isomer and thus lower ortho to para ratios are produced. The control of temperature, olefin ratio and pressure tend to suppress the rate of dealkylation and transalkylation and enhance the conditions for ortho alkylation.
By utilizing the above catalysts and exercizing control of the reaction parameters, ortho to para isomer ratios of 3:1 and higher, typically greater than 8:1 at conversions greater than 30% based upon aromatic feed, can easily be achieved. In any event the ratio of ortho to para isomer can be enhanced even with those catalyst systems generally suited for the production of high ortho to para ratios. To maximize production of the ortho-alkylated product reactor conditions are monitored and product analysis made. When the rate of decomposition of ortho-alkylated aromatic begins to exceed the rate of formation of ortho-alkylated aromatic amine, the reaction product is withdrawn from the reaction zone. Measurements may be plotted in graph form and rates determined.
Although not intending to be bound by theory, the observed regioselective ortho-alkylation of N-alkylates achieved by the practice of the invention is surprising since from prior art teachings one would expect a free carbenium ion derived from the olefin would result in a thermodynamically favored para-substituted product. Mechanisms were references and Hart-Kosak, J. Org. Chem., 27, 116 (1962) and J. Org. Chem., 22., 1752 (1957). Because of the observed regioselectivity by the practice of this invention we have concluded the ring nitrogen atom must exert a directing influence in forming ortho-alkylated product and this directing influence tends to overcome a counter reaction leading to the thermodynamically favored para-substituted product.
Experiments utilizing appropriately deuterium labelled olefins indicate that the primary mechanism of ortho-alkylation occurs via a concerted reaction between aromatic amine and olefin as shown in Scheme 1. Aniline is used as the illustrative amine and propylene is used as the illustrative olefin. ##STR3##
Para-alkylation, on the other hand, occurs differently than ortho-alkylation. Our evidence suggests a significant route to para-alkylation is through transalkylation of aniline via N-isopropylaniline. Scheme 2 below shows this mechanism. ##STR4##
This reaction scheme is supported by experimental work with N-n-propylaniline over 13% Al.sub.2 O.sub.3 /87% SiO.sub.2, wherein it was found that para-substitution occurred principally on the primary carbon while ortho-substitution occurred at the secondary carbon of the olefin. Although, transalkylation of either the ortho or para ring positions may occur, a clear preference for para alkylation was noted. It is believed the para-regioselectivity may be attributed to steric interference in the transition state as a result of the adjacent amino group. The following Scheme 3 summarizes this experimentation. ##STR5##
This working mechanism coupled with experimental observation indicates that a high molar ratio of olefin to aromatic amine favors a faster rate of ortho-alkylation of the aromatic amine relative to a slower transalkylation of aromatic amine with aromatic N-alkylate.
These reaction conditions used to produce ortho-alkylated aromatic amine can be summarized as those which use a solid phase acidic catalyst and utilize olefin and pressure to inhibit transalkylation and thereby suppress para formation.
The following examples are provided to illustrate various embodiments of the invention and are not intended to restrict the scope thereof.
EXAMPLE 1
A series of alkylation reactions was carried out in a fixed bed catalytic reactor, the reactor consisting of a 0.5" ID, 304 stainless steel tube which was jacketed with a single-element heater. A 5cc Vicor preheating bed was used to vaporize the reactants as they were passed downflow through the stainless steel tube jacketed reactor. The reactor was of sufficient length to accommodate from about 12-25 cubic centimeters of a solid phase catalyst system, having a particle size of from about 12-18 mesh (U.S. standard size). The reactions were conducted at temperatures ranging from about 100.degree.-400.degree. C. and pressures of from about 50-1000 psig and an LHSV based upon total aromatic amine liquid feed to the vaporizer of from 0.05 to 4.0 hr..sup.-1.
The reaction product was collected and byproduct olefin was removed via vaporization. The reaction product then was analyzed (free of olefin) by gas chromatography using an internal standard technique. Results are provided in Tables 1-6.
Temperatures, pressures, catalysts, moles, olefin and amine reactant, and other variables are recited in Table 1. Table 2 provides analytical results with respect to the run conditions described in Table 1. In Table 1 OBS is the sequential line observation for the particular table (there may be some skips); run is an arbitrary run number to permit rapid identification of that data set in other Tables; temperatures is in .degree.C., pressure is in psig, G-Al.sub.2 O.sub.3 refers to gamma-alumina, H-Y is a hydrogen exchanged Y zeolite, 13% Al.sub.2 O.sub.3 /SiO.sub.2 refers to a silica-alumina catalyst containing 13% by weight of Al.sub.2 O.sub.3. N refers to aromatic amine, i.e., aniline, R refers to olefin, i.e., propylene, X refers to N-alkylate, i.e., N-isopropylaniline, conversion (conv.) is expressed as % and is based upon the total moles ring alkylated product produced divided by the total moles of aromatic amine and N-alkylated amine feed times 100; and o-p, refers to the ortho-para ratio which is the moles of 2+2,6 isomers divided by the moles of 4 isomer+2,4-isomer+2,4,6-isomer. In some cases an ortho to para ratio of >40 has been written in, otherwise one would be dividing by zero. Tables 1 and 2 are arranged on the basis of ascending pressure. Tables 3 and 4 are duplicates of Tables 1 and 2 except they are arranged in ascending conversion. Tables 5 and 6 are duplicates of Tables 1 and 2 except they are arranged in ascending ortho para ratio.
Tables 1-6 illustrate the effect of various process parameters such as the mole ratio of olefin to total aromatic amine as well as the molar ratios of aniline to N-alkylate. They are to be used in combination to observe trends; e.g., O-P ratios vs. conversion based upon reaction parameters. No one specific value is to be considered as controlling but rather is to be considered in combination with another value. The table product legends are as follows:
1. Aniline - aniline
2. N-IPA - N-isopropylaniline
3. 2-IPA - ortho-isopropylaniline
4. 4-IPA - para-isopropylaniline
5. N-2-DIPA - N,2-diisopropylaniline
6. 2,4-DIPA - 2,4-diisopropylaniline
7. 2,6-DIPA - 2,6-diisopropylaniline
8. 2,4,6-TIPA - 2,4,6-triisopropylaniline
TABLE 1__________________________________________________________________________CONVERSION OF .sub.-- N-ISOPROPYLANILINEARRANGED IN ASCENDING PRESSURE BY CATALYST TYPE__________________________________________________________________________ Molar Feed RatioOBS SAMPLE ID RUN TEMPERATURE PRESSURE N R X CATALYST TYPE LHSV* CONV O-P__________________________________________________________________________1 7893-73-88 6 348 30 0.50 0.00 0.50 G-AL2O3 0.13 13.92 8.132 7893-73-89 7 348 30 0.50 0.00 0.50 G-AL2O3 0.13 14.38 7.933 7893-72-83 2 348 30 0.00 0.00 1.00 G-AL2O3 0.13 23.58 6.404 7893-72-82 1 348 30 0.00 0.00 1.00 G-AL2O3 0.13 24.16 6.375 7893-58-52 11 348 860 0.00 10.00 1.00 G-AL2O3 0.13 76.80 13.746 7893-73-86 5 348 900 0.50 0.00 0.50 G-AL2O3 0.13 6.97 >407 7893-75-92 9 348 900 0.75 2.00 0.25 G-AL2O3 0.13 12.38 14.278 7893-73-87 20 349 905 0.50 0.00 0.50 G-AL2O3 0.13 7.09 40.009 7893-75-93 22 349 910 0.75 2.00 0.25 G-AL2O3 0.13 9.66 14.5510 7893-75-94 23 349 910 0.75 2.00 0.25 G-AL2O3 0.13 12.61 >4011 7893-74-91 8 348 925 0.50 2.00 0.50 G-AL2O3 0.13 32.98 31.8212 7893-74-90 21 349 930 0.50 2.00 0.50 G-AL2O3 0.13 19.52 35.0813 7893-72-84 3 348 955 0.00 2.00 1.00 G-AL2O3 0.13 28.76 24.8314 7893-71-79 18 349 960 0.00 0.00 1.00 G-AL2O3 0.13 30.29 8.2915 7893-71-80 19 349 960 0.00 0.00 1.00 G-AL2O3 0.13 30.70 8.6116 7893-72-85 4 348 960 0.00 2.00 1.00 G-AL2O3 0.13 40.66 19.4517 7893-53-50 10 348 980 0.00 6.00 1.00 G-AL2O3 0.18 62.28 14.1918 7893-60-61 15 348 980 0.40 10.00 0.60 G-AL2O3 0.13 80.42 19.3519 7893-59-54 12 348 990 0.00 10.00 1.00 G-AL2O3 0.13 77.63 14.3520 7893-59-56 13 348 990 0.00 10.00 1.00 G-AL2O3 0.13 78.01 15.8221 7893-60-59 14 348 990 0.40 10.00 0.60 G-AL2O3 0.13 81.81 15.3926 7893-61-65 17 348 1000 0.40 10.00 0.60 G-AL2O3 0.13 83.85 14.5727 7893-61-63 16 348 1000 0.40 10.00 0.60 G-AL2O3 0.13 84.02 14.4728 7723-29-50 28 247 40 0.50 0.00 0.50 H-Y 0.18 9.44 1.0829 7723-29-51 29 247 40 0.50 0.00 0.50 H-Y 0.18 9.51 1.1530 7723-30-54 32 247 50 0.00 0.00 1.00 H-Y 0.18 8.76 2.7231 7723-30-56 33 247 50 0.00 0.00 1.00 H-Y 0.18 10.01 3.4932 7723-34-72 42 248 994 0.50 2.00 0.50 H-Y 0.75 21.23 8.5833 7723-34-71 41 248 997 0.50 2.00 0.50 H-Y 0.75 19.50 8.2934 7723-34-74 43 248 999 0.75 2.00 0.25 H-Y 0.75 10.40 9.43__________________________________________________________________________ *LHSV based on total aromatic feed only
Molar Feed RatioOBS SAMPLE ID RUN TEMPERATURE PRESSURE N R X CATALYST TYPE LHSV CONV O-P__________________________________________________________________________35 7723-33-70 40 248 999 0.50 2.00 0.50 H-Y 0.75 12.16 7.3636 7723-34-75 52 249 1003 0.75 2.00 0.25 H-Y 0.75 22.19 8.8837 7723-38-89 35 247 1013 0.00 0.00 1.00 H-Y 0.18 5.95 3.1038 7723-37-85 46 248 1013 0.75 2.00 0.25 H-Y 0.25 34.81 7.3139 7723-32-64 48 249 1014 0.50 2.00 0.50 H-Y 1.83 5.01 3.4340 7723-38-88 34 247 1014 0.00 0.00 1.00 H-Y 0.18 8.22 4.8741 7723-32-65 49 249 1015 0.50 2.00 0.50 H-Y 1.83 8.97 7.3642 7723-37-87 47 248 1026 0.75 2.00 0.25 H-Y 0.25 55.48 7.4143 7723-36-79 44 248 1033 0.50 2.00 0.50 H-Y 0.25 27.49 7.5344 7723-36-81 45 248 1035 0.50 2.00 0.50 H-Y 0.25 25.98 8.8445 7723-32-66 39 248 1038 0.50 2.00 0.50 H-Y 1.83 13.22 9.0946 7723-33-68 51 249 1054 0.00 2.00 1.00 H-Y 0.75 32.77 12.3447 7723-33-67 50 249 1060 0.00 2.00 1.00 H-Y 0.75 31.75 12.2748 7723-29-52 30 247 1067 0.50 0.00 0.50 H-Y 0.18 8.40 1.6649 7723-30-53 31 247 1068 0.50 0.00 0.50 H-Y 0.18 9.60 1.8250 7723-31-58 36 248 1071 0.00 2.00 1.00 H-Y 1.50 4.91 7.4751 7723-31-60 38 248 1073 0.00 2.00 1.00 H-Y 1.50 4.48 >4052 7723-31-59 37 248 1076 0.00 2.00 1.00 H-Y 1.50 4.57 >4053 7893-85-12 62 288 30 0.50 0.00 0.50 13% AL2O3/SIO2 0.18 15.53 2.6354 7893-85-11 54 287 30 0.50 0.00 0.50 13% AL2O3/SIO2 0.18 17.16 2.6355 7893-83-06 53 287 30 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 25.08 2.3456 7893-83-05 57 288 30 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 27.87 2.3061 7893-85-13 63 288 890 0.50 2.00 0.50 13% AL2O3/SIO2 1.17 26.69 9.2662 7893-85-14 64 289 890 0.50 2.00 0.50 13% AL2O3/SIO2 1.17 28.99 9.1763 7893-93-15 67 290 930 0.75 2.00 0.25 13% AL2O3/SIO2 2.20 16.97 13.3964 7893-93-16 68 290 930 0.75 2.00 0.25 13% AL2O3/SIO2 2.20 18.73 9.1265 7893-93-17 65 289 930 0.75 2.00 0.25 13% AL2O3/SIO2 1.10 32.45 8.4466 7893-93-18 66 289 930 0.75 2.00 0.25 13% AL2O3/SIO2 1.10 33.83 8.2867 7893-82-03 55 288 970 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 52.45 3.6468 7893-82-04 56 288 975 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 50.67 3.83__________________________________________________________________________
TABLE 2__________________________________________________________________________CONVERSION OF .sub.-- N-ISOPROPYLANILINE N-IPA 2-IPA 4-IPA ANILINE MOLE MOLE MOLE N,2-DIPA 2,4-DIPA 2,6-DIPA 2,4,6-TIPAOBS RUN MOLE PCT PCT PCT PCT MOLE PCT MOLE PCT MOLE PCT MOLE PCT CONV O-P__________________________________________________________________________1 6 83.98 2.10 9.21 1.13 0.00 0.00 0.00 0.00 13.92 8.132 7 84.98 0.72 9.06 1.14 0.00 0.00 0.00 0.00 14.38 7.933 2 74.80 1.62 13.78 1.67 0.00 0.55 0.45 0.00 23.58 6.404 1 72.91 2.93 14.07 1.69 0.00 0.60 0.51 0.00 24.16 6.375 11 17.81 5.39 43.65 1.20 4.08 2.16 19.66 1.54 76.80 13.746 5 56.66 36.36 3.78 0.00 0.00 0.00 0.00 0.00 6.97 >407 9 72.33 15.29 10.08 0.71 0.00 0.00 0.00 0.00 12.38 14278 20 57.32 35.59 3.42 0.00 0.00 0.00 0.00 0.00 7.09 >409 22 72.59 17.75 7.42 0.51 0.00 0.00 0.00 0.00 9.66 14.5510 23 69.12 18.27 10.10 0.00 0.42 0.00 0.54 0.00 12.61 >4011 8 47.84 19.18 23.67 0.00 2.36 0.98 5.23 0.00 32.98 31.8212 21 53.39 27.10 13.61 0.00 1.10 0.46 1.43 0.00 19.52 35.0813 3 41.85 29.38 18.16 0.00 2.52 0.99 3.87 0.00 28.76 24.8314 18 53.34 16.37 20.75 1.66 1.78 1.23 1.47 0.00 30.29 8.2915 19 53.72 15.58 21.45 1.69 1.75 1.17 1.42 0.00 30.70 8.6116 4 40.71 18.62 26.44 0.00 3.67 1.50 7.96 0.45 40.66 19.4517 10 29.42 8.30 39.30 0.73 3.60 2.02 14.30 1.28 62.28 14.1918 15 14.89 4.69 51.33 1.16 5.15 1.27 20.54 1.56 80.42 19.3519 12 16.97 5.39 48.76 1.17 4.68 2.20 18.99 1.68 77.63 14.3520 13 16.68 5.31 48.24 1.07 4.88 2.15 18.78 1.32 78.01 15.8221 14 13.79 4.40 50.27 1.20 5.08 2.18 21.78 1.63 81.81 15.3926 17 12.25 3.90 50.03 1.28 5.16 2.31 23.94 1.84 83.85 14.5727 16 12.11 3.88 49.54 1.30 5.11 2.29 24.18 1.87 84.02 14.4728 28 63.97 26.59 2.77 3.21 0.56 0.16 0.30 0.00 9.44 1.0829 29 62.85 27.64 2.91 3.30 0.56 0.00 0.33 0.00 9.51 1.1530 32 31.18 60.06 2.80 1.40 1.63 0.42 0.54 0.00 8.76 2.7231 33 30.02 59.97 3.48 1.44 2.27 0.37 0.57 0.00 10.01 3.4932 42 55.54 23.23 14.47 1.76 2.94 0.41 1.25 0.00 21.23 8.5833 41 57.77 22.74 13.02 1.65 2.53 0.35 1.04 0.00 19.50 8.2934 43 76.47 13.13 6.68 0.81 0.60 0.00 0.34 0.00 10.40 9.4335 40 66.21 21.64 7.20 1.23 1.49 0.00 0.38 0.00 12.16 7.3636 52 62.87 14.94 14.48 1.51 2.16 0.62 2.33 0.00 22.19 8.8837 35 62.97 31.08 2.70 1.19 0.57 0.00 0.41 0.00 5.95 3.1038 46 49.36 15.83 19.23 1.99 3.78 1.67 6.88 0.42 34.81 7.3139 48 73.31 21.68 1.82 0.64 0.39 0.00 0.00 0.00 5.01 3.4340 34 61.14 30.63 3.57 1.15 1.03 0.00 0.99 0.00 8.22 4.8741 49 68.30 22.72 5.50 0.90 1.15 0.00 0.00 0.00 8.97 7.3642 47 25.90 18.62 28.29 2.62 7.13 3.21 13.11 0.73 55.48 7.4143 44 50.34 22.18 18.56 2.41 3.66 0.85 2.33 0.00 27.49 7.5344 45 51.09 22.93 14.94 1.64 3.79 0.91 3.84 0.00 25.98 8.8445 39 63.70 23.09 7.96 1.11 1.75 0.00 0.38 0.00 13.22 9.0946 51 30.32 36.91 16.18 1.46 10.00 1.03 4.49 0.00 32.77 12.3447 50 31.37 36.88 16.46 1.44 8.87 0.97 4.22 0.00 31.75 12.2748 30 52.21 39.39 2.97 2.32 0.88 0.00 0.00 0.00 8.40 1.6649 31 53.29 37.12 3.63 2.72 1.00 0.00 0.32 0.00 9.60 1.8250 36 38.39 56.70 1.80 0.48 1.79 0.00 0.00 0.00 4.91 7.4751 38 40.17 55.34 1.80 0.00 1.53 0.00 0.00 0.00 4.48 >4052 37 40.23 55.20 1.75 0.00 1.60 0.00 0.00 0.00 4.57 >4053 62 76.44 8.03 11.61 3.30 0.63 1.72 0.97 0.00 15.53 2.6354 54 76.09 6.75 12.67 3.51 0.61 1.96 1.12 0.00 17.16 2.6355 53 60.45 14.47 14.47 3.86 2.00 3.39 2.15 0.71 25.08 2.3456 57 58.88 13.25 14.40 3.73 1.95 3.57 2.29 0.80 27.87 2.3061 63 42.05 31.26 11.34 1.22 6.76 0.93 1.80 0.00 26.69 9.2662 64 40.48 30.52 13.14 1.38 7.61 1.13 2.21 0.00 28.99 9.1763 67 63.67 19.35 11.48 1.16 3.04 0.00 1.00 0.00 16.97 13.3964 68 61.67 19.61 12.21 1.23 3.29 0.60 1.18 0.00 18.73 9.1265 65 48.47 19.08 19.44 1.58 5.41 1.53 3.56 0.26 32.45 8.4466 66 46.95 19.22 19.74 1.56 5.74 1.68 3.81 0.29 33.83 8.2867 55 33.23 14.33 24.96 2.80 6.47 5.92 7.15 1.88 52.45 3.6468 56 33.28 16.05 24.31 2.95 7.35 5.49 6.86 1.63 50.67 3.83__________________________________________________________________________
TABLE 3__________________________________________________________________________CONVERSION OF .sub.-- N-ISOPROPYLANILINEARRANGED IN ASCENDING CONVERSION BY CATALYST TYPE__________________________________________________________________________ Molar Feed RatioOBS SAMPLE ID RUN TEMPERATURE PRESSURE N R X CATALYST TYPE LHSV CONV O-P__________________________________________________________________________1 7893-73-86 5 348 900 0.50 0.00 0.50 G-AL2O3 0.13 6.97 >402 7893-73-87 20 349 905 0.50 0.00 0.50 G-AL2O3 0.13 7.09 >403 7893-75-93 22 349 910 0.75 2.00 0.25 G-AL2O3 0.13 9.66 14.554 7893-75-92 9 348 900 0.75 2.00 0.25 G-AL2O3 0.13 12.38 14.275 7893-75-94 23 349 910 0.75 2.00 0.25 G-AL2O3 0.13 12.61 >406 7893-73-88 6 348 30 0.50 0.00 0.50 G-AL2O3 0.13 13.92 8.137 7893-73-89 7 348 30 0.50 0.00 0.50 G-AL2O3 0.13 14.38 7.938 7893-74-90 21 349 930 0.50 2.00 0.50 G-AL2O3 0.13 19.52 35.089 7893-72-83 2 348 30 0.00 0.00 1.00 G-AL2O3 0.13 23.58 6.4010 7893-72-82 1 348 30 0.00 0.00 1.00 G-AL2O3 0.13 24.16 6.3711 7893-72-84 3 348 955 0.00 2.00 1.00 G-AL2O3 0.13 28.76 24.8312 7893-71-79 18 349 960 0.00 0.00 1.00 G-AL2O3 0.13 30.29 8.2913 7893-71-80 19 349 960 0.00 0.00 1.00 G-AL2O3 0.13 30.70 8.6114 7893-74-91 8 348 925 0.50 2.00 0.50 G-AL2O3 0.13 32.98 31.8215 7893-72-85 4 348 960 0.00 2.00 1.00 G-AL2O3 0.13 40.66 19.4520 7893-53-50 10 348 980 0.00 6.90 1.00 G-AL2O3 0.18 62.28 14.1921 7893-58-52 11 348 860 0.00 10.00 1.00 G-AL2O3 0.13 76.80 13.7422 7893-59-54 12 348 990 0.00 10.00 1.00 G-AL2O3 0.13 77.63 14.3523 7893-59-56 13 348 990 0.00 10.00 1.00 G-AL2O3 0.13 78.01 15.8224 7893-60-61 15 348 980 0.40 10.00 0.60 G-AL2O3 0.13 80.42 19.3525 7893-60-59 14 348 990 0.40 10.00 0.60 G-AL2O3 0.13 81.81 15.3926 7893-61-65 17 348 1000 0.40 10.00 0.60 G-AL2O3 0.13 83.85 14.5727 7893-61-63 16 348 1000 0.40 10.00 0.60 G-AL2O3 0.13 84.02 14.4728 7723-31-60 38 248 1073 0.00 2.00 1.00 H-Y 1.50 4.48 >4029 7723-31-59 37 248 1076 0.00 2.00 1.00 H-Y 1.50 4.57 >4030 7723-31-58 36 248 1071 0.00 2.00 1.00 H-Y 1.50 4.91 74731 7723-32-64 48 249 1014 0.50 2.00 0.50 H-Y 1.83 5.01 3.4332 7723-38-89 35 247 1013 0.00 0.00 1.00 H-Y 0.18 5.95 3.1033 7723-38-88 34 247 1014 0.00 0.00 1.00 H-Y 0.18 8.22 4.8734 7723-29-52 30 247 1067 0.50 0.00 0.50 H-Y 0.18 8.40 1.6635 7723-30-54 32 247 50 0.00 0.00 1.00 H-Y 0.18 8.76 2.7236 7723-32-65 49 249 1015 0.50 2.00 0.50 H-Y 1.83 8.97 7.3637 7723-29-50 28 247 40 0.50 0.00 0.50 H-Y 0.18 9.44 1.0838 7723-29-51 29 247 40 0.50 0.00 0.50 H-Y 0.18 9.51 1.1539 7723-30-53 31 247 1068 0.50 0.00 0.50 H-Y 0.18 9.60 1.8240 7723-30-56 33 247 50 0.00 0.00 1.00 H-Y 0.18 10.01 3.4941 7723-34-74 43 248 999 0.75 2.00 0.25 H-Y 0.75 10.40 9.4342 7723-33-70 40 248 999 0.50 2.00 0.50 H-Y 0.75 12.16 7.3643 7723-32-66 39 248 1038 0.50 2.00 0.50 H-Y 1.83 13.22 9.0944 7723-34-71 41 248 997 0.50 2.00 0.50 H-Y 0.75 19.50 8.2945 7723-34-72 42 248 994 0.50 2.00 0.50 H-Y 0.75 21.23 8.5846 7723-34-75 52 249 1003 0.75 2.00 0.25 H-Y 0.75 22.19 8.8847 7723-36-81 45 248 1035 0.50 2.00 0.50 H-Y 0.25 25.98 8.8448 7723-36-79 44 248 1033 0.50 2.00 0.50 H-Y 0.25 27.49 7.5349 7723-33-67 50 249 1060 0.00 2.00 1.00 H-Y 0.75 31.75 12.2750 7723-33-68 51 249 1054 0.00 2.00 1.00 H-Y 0.75 32.77 12.3451 7723-37-85 46 248 1013 0.75 2.00 0.25 H-Y 0.25 34.81 7.3152 7723-37-87 47 248 1026 0.75 2.00 0.25 H-Y 0.25 55.48 7.4153 7893-85-12 62 288 30 0.50 0.00 0.50 13% AL2O3/SIO2 0.18 15.53 2.6354 7893-93-15 67 290 930 0.75 2.00 0.25 13% AL2O3/SIO2 2.20 16.97 13.3955 7893-85-11 54 287 30 0.50 0.00 0.50 13% AL2O3/SIO2 0.18 17.16 2.6357 7893-93-16 68 290 930 0.75 2.00 0.25 13% AL2O3/SIO2 2.20 18.73 9.1259 7893-83-06 53 287 30 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 25.08 2.3460 7893-85-13 63 288 890 0.50 2.00 0.50 13% AL2O3/SIO2 1.17 26.69 9.2661 7893-83-05 57 288 30 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 27.87 2.3062 7893-85-14 64 289 890 0.50 2.00 0.50 13% AL2O3/SIO2 1.17 28.99 9.1763 7893-93-17 65 289 930 0.75 2.00 0.25 13% AL2O3/SIO2 1.10 32.45 8.4464 7893-93-18 66 289 930 0.75 2.00 0.25 13% AL2O3/SIO2 1.10 33.83 8.2865 7893-82-04 56 288 975 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 50.67 3.8366 7893-82-03 55 288 970 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 52.45 3.64__________________________________________________________________________
TABLE 4__________________________________________________________________________CONVERSION OF .sub.-- N-ISOPROPYLANILINE N-IPA 2-IPA 4-IPA ANILINE MOLE MOLE MOLE N,2-DIPA 2,4-DIPA 2,6-DIPA 2,4,6-TIPAOBS RUN MOLE PCT PCT PCT PCT MOLE PCT MOLE PCT MOLE PCT MOLE PCT CONV O-P__________________________________________________________________________1 5 56.66 36.36 3.78 0.00 0.00 0.00 0.00 0.00 6.97 >402 20 57.32 35.59 3.42 0.00 0.00 0.00 0.00 0.00 7.09 >403 22 72.59 17.75 7.42 0.51 0.00 0.00 0.00 0.00 9.66 14.554 9 72.33 15.29 10.08 0.71 0.00 0.00 0.00 0.00 12.38 14.275 23 69.12 18.27 10.10 0.00 0.42 0.00 0.54 0.00 12.61 >406 6 83.98 2.10 9.21 1.13 0.00 0.00 0.00 0.00 13.92 8.137 7 84.89 0.72 9.06 1.14 0.00 0.00 0.00 0.00 14.38 7.938 21 53.39 27.10 13.61 0.00 1.10 0.46 1.43 0.00 19.52 35.089 2 74.80 1.62 13.78 1.67 0.00 0.55 0.45 0.00 23.58 6.4010 1 72.91 2.93 14.07 1.69 0.00 0.60 0.51 0.00 24.16 6.3711 3 41.85 29.38 18.16 0.00 2.52 0.99 3.87 0.00 28.76 24.8312 18 53.34 16.37 20.75 1.66 1.78 1.23 1.47 0.00 30.29 8.2913 19 53.72 15.58 21.45 1.69 1.75 1.17 1.42 0.00 30.70 8.6114 8 47.84 19.18 23.67 0.00 2.36 0.98 5.23 0.00 32.98 31.8215 4 40.71 18.62 26.44 0.00 3.67 1.50 7.96 0.45 40.66 19.4520 10 29.42 8.30 39.30 0.73 3.60 2.02 14.30 1.28 62.28 14.1921 11 17.81 5.39 43.65 1.20 4.08 2.16 19.66 1.54 76.80 13.7422 12 16.97 5.39 48.76 1.17 4.68 2.20 18.99 1.68 77.63 14.3523 13 16.68 5.31 48.24 1.07 4.88 2.15 18.78 1.32 78.01 15.8224 15 14.89 4.69 51.33 1.16 5.15 1.27 20.54 1.56 80.42 19.3525 14 13.79 4.40 50.27 1.20 5.08 2.18 21.78 1.63 81.81 15.3926 17 12.25 3.90 50.03 1.28 5.16 2.31 23.94 1.84 83.85 14.5727 16 12.11 3.88 49.54 1.30 5.11 2.29 24.18 1.87 84.02 14.4728 38 40.17 55.34 1.80 0.00 1.53 0.00 0.00 0.00 4.48 >4029 37 40.23 55.20 1.75 0.00 1.60 0.00 0.00 0.00 4.57 >4030 36 38.39 56.70 1.80 0.48 1.79 0.00 0.00 0.00 4.91 7.4731 48 73.31 21.68 1.82 0.64 0.39 0.00 0.00 0.00 5.01 3.4332 35 62.97 31.08 2.70 1.19 0.57 0.00 0.41 0.00 5.95 3.1033 34 61.14 30.63 3.57 1.15 1.03 0.00 0.99 0.00 8.22 4.8734 30 52.21 39.39 2.97 2.32 0.88 0.00 0.00 0.00 8.40 1.6635 32 31.18 60.06 2.80 1.40 1.63 0.42 0.54 0.00 8.76 2.7236 49 68.30 22.72 5.50 0.90 1.15 0.00 0.00 0.00 8.97 7.3637 28 63.97 26.59 2.77 3.21 0.56 0.16 0.30 0.00 9.44 1.0838 29 62.85 27.64 2.91 3.30 0.56 0.00 0.33 0.00 9.51 1.1539 31 53.29 37.12 3.63 2.72 1.00 0.00 0.32 0.00 9.60 1.8240 33 30.02 59.97 3.48 1.44 2.27 0.37 0.57 0.00 10.01 3.4941 43 76.47 13.13 6.68 0.81 0.60 0.00 0.34 0.00 10.40 9.4342 40 66.21 21.64 7.20 1.23 1.49 0.00 0.38 0.00 12.16 7.3643 39 63.70 23.09 7.96 1.11 1.75 0.00 0.38 0.00 13.22 9.0944 41 57.77 22.74 13.02 1.65 2.53 0.35 1.04 0.00 19.50 8.2945 42 55.54 23.23 14.47 1.76 2.94 0.41 1.25 0.00 21.23 8.5846 52 62.87 14.94 14.48 1.51 2.16 0.62 2.33 0.00 22.19 8.8847 45 51.09 22.93 14.94 1.64 3.79 0.91 3.84 0.00 25.98 8.8448 44 50.34 22.18 18.56 2.41 3.66 0.85 2.33 0.00 27.49 7.5349 50 31.37 36.88 16.46 1.44 8.87 0.97 4.22 0.00 31.75 12.2750 51 30.32 36.91 16.18 1.46 10.00 1.03 4.49 0.00 32.77 12.3451 46 49.36 15.83 19.23 1.99 3.78 1.67 6.88 0.42 34.81 7.3152 47 25.90 18.62 28.29 2.62 7.13 3.21 13.11 0.73 55.48 7.4153 62 76.44 8.03 11.61 3.30 0.63 1.72 0.97 0.00 15.53 2.6354 67 63.67 19.35 11.48 1.16 3.04 0.00 1.00 0.00 16.97 13.3955 54 76.09 6.75 12.67 3.51 0.61 1.96 1.12 0.00 17.16 2.6357 68 61.67 19.61 12.21 1.23 3.29 0.60 1.18 0.00 18.73 9.1259 53 60.45 14.47 14.47 3.86 2.00 3.39 2.15 0.71 25.08 2.3460 63 42.05 31.26 11.34 1.22 6.76 0.93 1.80 0.00 26.69 9.2661 57 58.88 13.25 14.40 3.73 1.95 3.57 2.29 0.80 27.87 2.3062 64 40.48 30.52 13.14 1.39 7.61 1.13 2.21 0.00 28.99 9.1763 65 48.47 19.08 19.44 1.58 5.41 1.53 3.56 0.26 32.45 8.4464 66 46.95 19.22 19.74 1.56 5.74 1.68 3.81 0.29 33.83 8.2865 56 33.28 16.05 24.31 2.95 7.35 5.49 6.86 1.63 50.67 3.8366 55 33.23 14.33 24.96 2.80 6.47 5.92 7.15 1.88 52.45 3.64__________________________________________________________________________
TABLE 5__________________________________________________________________________CONVERSION OF .sub.-- N-ISOPROPYLANILINEARRANGED IN ASCENDING ORTHO-PARA RATIO BY CATALYST TYPE__________________________________________________________________________ Molar Feed RatioOBS SAMPLE ID RUN TEMPERATURE PRESSURE N R X CATALYST TYPE LHSV CONV O-P__________________________________________________________________________1 7893-73-86 5 348 900 0.50 0.00 0.50 G-AL2O3 0.13 6.97 >402 7893-73-87 20 349 905 0.50 0.00 0.50 G-AL2O3 0.13 7.09 >403 7893-75-94 23 349 910 0.75 2.00 0.25 G-AL2O3 0.13 12.61 >404 7893-72-82 1 348 30 0.00 0.00 1.00 G-AL2O3 0.13 24.16 6.375 7893-72-83 2 348 30 0.00 0.00 1.00 G-AL2O3 0.13 23.58 6.408 7893-73-89 7 348 30 0.50 0.00 0.50 G-AL2O3 0.13 14.38 7.939 7893-73-88 6 348 30 0.50 0.00 0.50 G-AL2O3 0.13 13.92 8.1310 7893-71-79 18 349 960 0.00 0.00 1.00 G-AL2O3 0.13 30.29 8.2912 7893-71-80 19 349 960 0.00 0.00 1.00 G-AL2O3 0.13 30.70 8.6114 7893-58-52 11 348 860 0.00 10.00 1.00 G-AL2O3 0.13 76.80 13.7415 7893-53-50 10 348 980 0.00 6.90 1.00 G-AL2O3 0.18 62.28 14.1916 7893-75-92 9 348 900 0.75 2.00 0.25 G-AL2O3 0.13 12.38 14.2717 7893-59-54 12 348 990 0.00 10.00 1.00 G-AL2O3 0.13 77.63 14.3518 7893-61-63 16 348 1000 0.40 10.00 0.60 G-AL2O3 0.13 84.02 14.4719 7893-75-93 22 349 910 0.75 2.00 0.25 G-AL2O3 0.13 9.66 14.5520 7893-61-65 17 348 1000 0.40 10.00 0.60 G-AL2O3 0.13 83.85 14.5721 7893-60-59 14 348 990 0.40 10.00 0.60 G-AL2O3 0.13 81.81 15.3922 7893-59-56 13 348 990 0.00 10.00 1.00 G-AL2O3 0.13 78.01 15.8223 7893-60-61 15 348 980 0.40 10.00 0.60 G-AL2O3 0.13 80.42 19.3524 7893-72-85 4 348 960 0.00 2.00 1.00 G-AL2O3 0.13 40.66 19.4525 7893-72-84 3 348 955 0.00 2.00 1.00 G-AL2O3 0.13 28.76 24.8326 7893-74-91 8 348 925 0.50 2.00 0.50 G-AL2O3 0.13 32.98 31.8227 7893-74-90 21 349 930 0.50 2.00 0.50 G-AL2O3 0.13 19.52 35.0828 7723-31-59 37 248 1076 0.00 2.00 1.00 H-Y 1.50 4.57 >4029 7723-31-60 38 248 1073 0.00 2.00 1.00 H-Y 1.50 4.48 >4030 7723-29-50 28 247 40 0.50 0.00 0.50 H-Y 0.18 9.44 1.0831 7723-29-51 29 247 40 0.50 0.00 0.50 H-Y 0.18 9.51 1.1532 7723-29-52 30 247 1067 0.50 0.00 0.50 H-Y 0.18 8.40 1.6633 7723-30-53 31 247 1068 0.50 0.00 0.50 H-Y 0.18 9.60 1.8234 7723-30-54 32 247 50 0.00 0.00 1.00 H-Y 0.18 8.76 2.7235 7723-38-89 35 247 1013 0.00 0.00 1.00 H-Y 0.18 5.95 3.1036 7723-32-64 48 249 1014 0.50 2.00 0.50 H-Y 1.83 5.01 3.4337 7723-30-56 33 247 50 0.00 0.00 1.00 H-Y 0.18 10.01 3.4938 7723-38-88 34 247 1014 0.00 0.00 1.00 H-Y 0.18 8.22 4.8739 7723-37-85 46 248 1013 0.75 2.00 0.25 H-Y 0.25 34.81 7.3140 7723-33-70 40 248 999 0.50 2.00 0.50 H-Y 0.75 12.16 7.3641 7723-32-65 49 249 1015 0.50 2.00 0.50 H-Y 1.83 8.97 7.3642 7723-37-87 47 248 1026 0.75 2.00 0.25 H-Y 0.25 55.48 7.4143 7723-31-58 36 248 1071 0.00 2.00 1.00 H-Y 1.50 4.91 7.4744 7723-36-79 44 248 1033 0.50 2.00 0.50 H-Y 0.25 27.49 7.5345 7723-34-71 41 248 997 0.50 2.00 0.50 H-Y 0.75 19.50 8.2946 7723-34-72 42 248 994 0.50 2.00 0.50 H-Y 0.75 21.23 8.5847 7723-36-81 45 248 1035 0.50 2.00 0.50 H-Y 0.25 25.98 8.8448 7723-34-75 52 249 1003 0.75 2.00 0.25 H-Y 0.75 22.19 8.8849 7723-32-66 39 248 1038 0.50 2.00 0.50 H-Y 1.83 13.22 9.0950 7723-34-74 43 248 999 0.75 2.00 0.25 H-Y 0.75 10.40 9.4351 7723-33-67 50 249 1060 0.00 2.00 1.00 H-Y 0.75 31.75 12.2752 7723-33-68 51 249 1054 0.00 2.00 1.00 H-Y 0.75 32.77 12.3453 7893-83-05 57 288 30 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 27.87 2.3054 7893-83-06 53 287 30 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 25.08 2.3455 7893-85-12 62 288 30 0.50 0.00 0.50 13% AL2O3/SIO2 0.18 15.53 2.6356 7893-85-11 54 287 30 0.50 0.00 0.50 13% AL2O3/SIO2 0.18 17.16 2.6357 7893-82-03 55 288 970 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 52.45 3.6458 7893-82-04 56 288 975 0.00 0.00 1.00 13% AL2O3/SIO2 0.18 50.67 3.8363 7893-93-18 66 289 930 0.75 2.00 0.25 13% AL2O3/SIO2 1.10 33.83 8.2864 7893-93-17 65 289 930 0.75 2.00 0.25 13% AL2O3/SIO2 1.10 32.45 8.4465 7893-93-16 68 290 930 0.75 2.00 0.25 13% AL2O3/SIO2 2.20 18.73 9.1266 7893-85-14 64 289 890 0.50 2.00 0.50 13% AL2O3/SIO2 1.17 28.99 9.1767 7893-85-13 63 288 890 0.50 2.00 0.50 13% AL2O3/SIO2 1.17 26.69 9.2668 7893-93-15 67 290 930 0.75 2.00 0.25 13% AL2O3/SIO2 2.20 16.97 13.39__________________________________________________________________________
TABLE 6__________________________________________________________________________CONVERSION OF .sub.-- N-ISOPROPYLANILINE N-IPA 2-IPA 4-IPA ANILINE MOLE MOLE MOLE N,2-DIPA 2,4-DIPA 2,6-DIPA 2,4,6-TIPAOBS RUN MOLE PCT PCT PCT PCT MOLE PCT MOLE PCT MOLE PCT MOLE PCT CONV O-P__________________________________________________________________________1 5 56.66 36.36 3.78 0.00 0.00 0.00 0.00 0.00 6.97 >402 20 57.32 35.59 3.42 0.00 0.00 0.00 0.00 0.00 7.09 >403 23 69.12 18.27 10.10 0.00 0.42 0.00 0.54 0.00 12.61 >614 1 72.91 2.93 14.07 1.69 0.00 0.60 0.51 0.00 24.16 6.375 2 74.80 1.62 13.78 1.67 0.00 0.55 0.45 0.00 23.58 6.408 7 84.89 0.72 9.06 1.14 0.00 0.00 0.00 0.00 14.38 7.939 6 83.98 2.10 9.21 1.13 0.00 0.00 0.00 0.00 13.92 8.1310 18 53.34 16.37 20.75 1.66 1.78 1.23 1.47 0.00 30.29 8.2912 19 53.72 15.58 21.45 1.69 1.75 1.17 1.42 0.00 30.70 8.6114 11 17.81 5.39 43.65 1.20 4.08 2.16 19.66 1.54 76.80 13.7415 10 29.42 8.30 39.30 0.73 3.60 2.02 14.30 1.28 62.28 14.1916 9 72.33 15.29 10.08 0.71 0.00 0.00 0.00 0.00 12.38 14.2717 12 16.97 5.39 48.76 1.17 4.68 2.20 18.99 1.68 77.63 14.3518 16 12.11 3.88 49.54 1.30 5.11 2.29 24.18 1.87 84.02 14.4719 22 72.59 17.75 7.42 0.51 0.00 0.00 0.00 0.00 9.66 14.5520 17 12.25 3.90 50.03 1.28 5.16 2.31 23.94 1.84 83.85 14.5721 14 13.79 4.40 50.27 1.20 5.08 2.18 21.78 1.63 81.81 15.3922 13 16.68 5.31 48.24 1.07 4.88 2.15 18.78 1.32 78.01 15.8223 15 14.89 4.69 51.33 1.16 5.15 1.27 20.54 1.56 80.42 19.3524 4 40.71 18.62 26.44 0.00 3.67 1.50 7.96 0.45 40.66 19.4525 3 41.85 29.38 18.16 0.00 2.52 0.99 3.87 0.00 28.76 24.8326 8 47.84 19.18 23.67 0.00 2.36 0.98 5.23 0.00 32.98 31.8227 21 53.39 27.10 13.61 0.00 1.10 0.46 1.43 0.00 19.52 35.0828 37 40.23 55.20 1.75 0.00 1.60 0.00 0.00 0.00 4.57 >4029 38 40.17 55.34 1.80 0.00 1.53 0.00 0.00 0.00 4.48 >4030 28 63.97 26.59 2.77 3.21 0.56 0.16 0.30 0.00 9.44 1.0831 29 62.85 27.64 2.91 3.30 0.56 0.00 0.33 0.00 9.51 1.1532 30 52.21 39.39 2.97 2.32 0.88 0.00 0.00 0.00 8.40 1.6633 31 53.29 37.12 3.63 2.72 1.00 0.00 0.32 0.00 9.60 1.8234 32 31.18 60.06 2.80 1.40 1.63 0.42 0.54 0.00 8.76 2.7235 35 62.97 31.08 2.70 1.19 0.57 0.00 0.41 0.00 5.95 3.1036 48 73.31 21.68 1.82 0.64 0.39 0.00 0.00 0.00 5.01 3.4337 33 30.02 59.97 3.48 1.44 2.27 0.37 0.57 0.00 10.01 3.4938 34 61.14 30.63 3.57 1.15 1.03 0.00 0.99 0.00 8.22 4.8739 46 49.36 15.83 19.23 1.99 3.78 1.67 6.88 0.42 34.81 7.3140 40 66.21 21.64 7.20 1.23 1.49 0.00 0.38 0.00 12.16 7.3641 49 68.30 22.72 5.50 0.90 1.15 0.00 0.00 0.00 8.97 7.3642 47 25.90 18.62 28.29 2.62 7.13 3.21 13.11 0.73 55.48 7.4143 36 38.39 56.70 1.80 0.48 1.79 0.00 0.00 0.00 4.91 7.4744 44 50.34 22.18 18.56 2.41 3.66 0.85 2.33 0.00 27.49 7.5345 41 57.77 22.74 13.02 1.65 2.53 0.35 1.04 0.00 19.50 8.2946 42 55.54 23.23 14.47 1.76 2.94 0.41 1.25 0.00 21.23 8.5847 45 51.09 22.93 14.94 1.64 3.79 0.91 3.84 0.00 25.98 8.8448 52 62.87 14.94 14.48 1.51 2.16 0.62 2.33 0.00 22.19 8.8849 39 63.70 23.09 7.96 1.11 1.75 0.00 0.38 0.00 13.22 9.0950 43 76.47 13.13 6.68 0.81 0.60 0.00 0.34 0.00 10.40 9.4351 50 31.37 36.88 16.46 1.44 8.87 0.97 4.22 0.00 31.75 12.2752 51 30.32 36.91 16.18 1.46 10.00 1.03 4.49 0.00 32.77 12.3453 57 58.88 13.25 14.40 3.73 1.95 3.57 2.29 0.80 27.87 2.3054 53 60.45 14.47 14.47 3.86 2.00 3.39 2.15 0.71 25.08 2.3455 62 76.44 8.03 11.61 3.30 0.63 1.72 0.97 0.00 15.53 2.6356 54 76.09 6.75 12.67 3.51 0.61 1.96 1.12 0.00 17.16 2.6357 55 33.23 14.33 24.96 2.80 6.47 5.92 7.15 1.88 52.45 3.6458 56 33.28 16.05 24.31 2.95 7.35 5.49 6.86 1.63 50.67 3.8363 66 46.95 19.22 19.74 1.56 5.74 1.68 3.81 0.29 33.83 8.2864 65 48.47 19.08 19.44 1.58 5.41 1.53 3.56 0.26 32.45 8.4465 68 61.67 19.61 12.21 1.23 3.29 0.60 1.18 0.00 18.73 9.1266 64 40.48 30.52 13.14 1.39 7.61 1.13 2.21 0.00 28.99 9.1767 63 42.05 31.26 11.34 1.22 6.76 0.93 1.80 0.00 26.69 9.2668 67 63.67 19.35 11.48 1.16 3.04 0.00 1.00 0.00 16.97 13.39__________________________________________________________________________
Review of the data Tables 1 and 3 show that addition of aromatic amine to N-alkylate at comparable pressure increases the relative amount of N-alkylate in the product stream; i.e., reduces conversion when reaction conditions are kept constant. The data suggest N-alkylation and ring alkylation are competing reactions. Thus, diluting N-alkylate with aniline, without adding olefin, will increase para-alkylation rather than decrease it at comparable conversion. Compare runs 35, 30, and 39 (OBS 37, 48, 45). The data suggest that appropriate steps can be taken to control the reaction of N-alkylates in terms of ortho-regioselectivity required in ring alkylation.
The data in Table 1 clearly illustrate the importance of maintaining a positive olefin molar ratio and not simply increasing the reaction pressure in the conversion of N-alkylate to ortho-alkylated product. This is particularly true in the case of the H-Y and silica-alumina catalyst which have a capability of producing higher levels of the para-isomer than does gamma-alumina. Gamma-alumina is rather unique in itself. Run 2 and Run 18 (OBS 3 and 14) illustrate, as a general rule, when one increases the pressure of the reaction without adding olefin, there is a tendency to produce only a slight increase in the ortho-para isomer ratio. These runs show that going from 30-960 psig with no olefin present, the ortho-para ratio went from about 6 to 8:1 and conversion increased from 23 to 34%. Also compare runs 28, 29, 30, and 31 (OBS 28, 29, 37 and 48). These runs show that when no olefin was present and at 40 psig the catalyst gave about 10% conversion with an ortho-para ratio of 1:1 (Runs 28 and 29) and about the same when the pressure was increased to about 1000 psig (OBS 37, 48). One can essentially double and triple the ortho-para ratio as compared to the previous runs under identical conditions by using a high positive pressure with the addition of olefin, e.g., 1000 psig of olefin with the olefin being present in a molar ratio of at least 2 moles olefin per mole of amine feedstock. Runs 28-33 and runs 4, 40, 42 and 43 are illustrative (OBS 28, 29, 30, 31, 49, 35, 32 and 34).
Tables 3 and 4, which are arranged in order of ascending conversion show that conversions in excess of 30% and at ortho to para isomer ratios in excess of 6:1 are obtained. When a high positive pressure of propylene is present, conversion and the ortho-para ratio increases dramatically. For example conversion can be increased from 30% to about 75% and the ortho-para ratio can be increased from 8 to about 15:1. Also note para-alkylation from N-isopropylaniline can be held to a minimum by the maintenance of a high olefin to aniline/N-isopropylaniline molar ratio (runs 25, 27, 17 and 16, (OBS 17, 18, 26 and 27) compared to runs 5 and 20 (OBS 1, 2).
The trends with respect to conversion and ortho-para ratio set forth with gamma-alumina holds true for both the H-Y and silica-alumina catalyst. As with gamma alumina, the H-Y and silica-alumina catalysts show conversion increases with high olefin pressure and the transalkylation to the para isomer is minimized thereby maintaining a high ortho-para ratio. (Runs 35, 34, 52, 44 and 50 are illustrative) (OBS 32, 33, 46, 48 and 49).
Tables 5 and 6 are arranged in ascending order of ortho to para ratio and highlight that feature of the invention by showing high ortho to para ratios can be obtained at high conversion. Many of the runs discussed with respect to Tables 1-4 become easy to isolate in reviewing the ortho to para sorting followed by a review of the corresponding conversion values.
The H-Y catalyst runs demonstrate the effect of LHSV on conversion of N-alkylates. It can be readily seen that the degree of conversion is dependent on residence time. Longer residence time, i.e., lower LHSV, brings about higher conversion of N-alkylates. Compare runs 51 and 36 (OBS 46 and 50).

Number	Name	Date
2115884	Schollkopf	May 1938
2762845	Stroh et al.	Sep 1956
2923745	Buls et al.	Feb 1960
3275690	Stroh et al.	Sep 1966
3649693	Napolitano	Mar 1972
3701811	Nicklin	Oct 1972
3733365	Yeakey et al.	May 1973
3923892	Klopfer	Dec 1975
4351958	Takahata	Sep 1982
4446329	Waller	May 1984

Number	Date	Country
1051271	Feb 1959	DEX
38-4569	Apr 1963	JPX
59-167545	Sep 1984	JPX
421791	Dec 1934	GBX
846226	Aug 1960	GBX

Formation of ortho-alkylated aromatic amines from N-alkylated aromatic amines

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Non-Patent Literature Citations (6)

Entry
Chemical Abstracts, (43), 4644(f), (1949), Lavrovskii et al.
Chemical Abstracts (94), 163245p, (1981), Zarubina et al.
Chemical Abstracts, (83), 134815s, (1975), Borukhova et al.
Hart-Kosak, J. Org. Chem., 27, 116 (1962).
Hart-Kosak, J. Org. Chem., 22, 1752 (1957).
Reilly and Hickenbottom, J. Chem., Soc., 117, 103, (1920).