Alkylations toluene

The same type catalyst modified with boron (41), magnesium (42), or phosphoms (43) to reduce the pore size can be used to alkylate toluene with ethylene to produce predominantly -ethyltoluene. Since -ethyltoluene [622-96-8] has the smallest effective diameter of the ethyltoluene isomers, the selectivity to this isomer is favored because it can most easily escape the ZSM-5 pore stmcture. For the same reason, the alkylation of toluene [108-88-3] to xylene [106 2-3] also is favored over the usual acid catalyzed equiHbrium mixture of isomers when it is carried out over magnesium- or phosphoms-modified ZSM-5 (44). 

A munber of organic compounds are suitable for use as tracers in a process for monitoring the flow of subterranean fluids. The following traces have been proposed benzene tetracarboxylic acid, methylbenzoic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthalene-trisulfonic acid, alkyl benzene sulfonic acid, alkyl toluene sulfonic acid, alkyl xylene sulfonic acid, a-olefin sulfonic acid, salts of the foregoing acids, naphthalenediol, aniline, substituted aniline, pyridine, substituted pyridines [883]. 

DETOL [De-alkylation of toluene] A process for making benzene by de-alkylating toluene and other aromatic hydrocarbons. Developed by the Houdiy Process and Chemical Company, and generally similar to its Litol process for the same purpose. The catalyst is chromia/alumina. Licensed by Air Products Chemicals. In 1987,12 plants had been licensed. 

Explanation The increase of both Y and DP with time implies a growing species of long life, which is characteristic of esters but not of carbenium ions, and an absence of transfer reactions. The suppression of all kinds of transfer reactions seems to require some very special features in the anionoid moiety of the ester which are not yet understood fully but which, by hypothesis, cannot affect the reaction pattern of an isolated, unpaired cation. The fact that living polymerisations can occur in toluene is a convincing demonstration that these reactions cannot involve carbenium ions, because growing cations alkylate toluene [33-37], a process which produces low DPs, independent of Y. 

Uu, H.-C. (1985) Modified zeolite catalyst composition and process for alkylating toluene with methanol to form styrene. U.S. Patent 4, 499,318. 

Superhydride has also been used for the hydrogenolysis of alkyl toluene-p-sulphonates, and an illustrative example is given in Expt 5.4 for the preparation of cyclooctane from cyclooctyl toluene-p-sulphonate. A sodium borohydride hydrogenolysis of alkyl halides and of alkyl methane- and toluene-p-sulphonates under PTC conditions provides an interesting variant of this reaction.9... 

Notes. (1) A procedure for the preparation of alkyl toluene-p-sulphonates is described in Expt 6.46. 

The Grignard reagent derived from benzyl chloride undergoes ready alkylation with an alkyl toluene-p-sulphonate, a reaction which provides a further useful synthesis of an alkylbenzene (e.g. pentylbenzene, Expt 6.2). 

The substrates are secondary alkyl -toluene sulfonates, and so we expect elimination to compete with substitution. Compound B is formed in both reactions and has the molecular formula of 4-ferf-butylcyclohexene. Because the two p-toluenesulfonates are diastereomers, it is likely that compounds A and C, especially since they have the same molecular formula, are also diastereomers. Assuming that the substitution reactions proceed with inversion of configuration, we conclude that the products are as shown. 

Of the processes likely to favor its production, only the one proposed by Mobil currently appears capable of industrialization. This is because, among the different forms of zeolite developed by this company, tbe catalyst HZSM5, modified by magnesium mid phosphorus, is capable of alkylating toluene by ethylene with a high para isomer selectivity. Thus, a 95/5 blend of p- and m>methylethylbenzenes can be obtained, which considerably simplifies separation problems and yields p-meth styrene by dehydrogena ... 

Alkoxides are nucleophiles and may be used to react with alkyl hahdes or alkyl toluene-4-sulfonates to form ethers (Scheme 2.1 Ic). 

Oxidation of alkyltoluenes, A Shell Oil group has studied the oxidation of alkyl-toluenes by oxygen in the presence of cobalt(ll) acetate as catalyst. The reaction involves the continuous conversion of Co(ll) ions to Co(lll) ions promoted by methyl ethyl ketone. The methyl group is preferentially oxidized. Thusp-cymene affordsp-isopropyl-benzoicacid (90% yield) and p-acetobenzoic acid (10% yield). The relative ease of... 

The recent studies on the relationship between activation temperature and carbonium ion type catalytic activity of both decationized and cation exchanged zeolites show that at arid above the temperature required for the removal of all observable hydroxyls with vibrational frequencies between 3700-3500 cm" the activity sharply declines. The lowest concentration of acidic lattice hydroxyl required for carbonium ion activity seems to depend on the reaction involved. For example, dehydroxylation of La-exchanged Y to a level at which hydroxyl content was unobservable by currently-used infrared techniques led to total loss of activity to crack n-butane, but only partial loss of activity to crack cumene (vide infra) and to alkylate toluene with propylene (74). The activity and hydroxyl content lost on dehydroxylation can be restored upon subsequent treatment with water (11). Furthermore, alkali metal zeolites, which have little or no carbonium ion type activity can be made to show strong activity by the addition of a proton source, such as alkyl chlorides (51, 58). The similarity of the products obtained with the... 

Friedel-Crafts alkylation reactions are, in general, accompanied by isomerization processes. Olah et a/. reported the results of the water-promoted, AlCb-catalyzed isomerization of o-, m- and p-di-f-bu-tylbenzene. No ortho isomer was present in the equilibrium mixture. The isomerization of o-di-r-bu-tylbenzene was very rapid largely due to relief of steric strain. In these and other related sterically hindered arenes, intramolecular isomerization and not dealkylation was observed. Isomerization of di-and mono-methylnaphthalenes, catalyzed by HF-BF3, was also reported. Isomerization of /i-alkyl-toluenes and -xylenes, catalyzed by AICI3 at room temperature, afforded chiefly /n-/i-alkyltoluenes and /n-/i-alkylxylenes, respectively. The process leading to the meta isomer has a lower energy than the other processes. 

With all the zeolites 1-heptene isomerizes into 2 and 3-heptenes, monoheptyltoluenes are formed by alkylation of toluene with heptenes, biheptyltoluenes by allQdation of monoheptyltoluenes. Non desorbed products are also found. Neither skeletal isomerization and dimerization of heptenes nor formation of Cl4 alkyl toluene are observed. 

Fig. 11. Long chain alkyl aromatic normal patterns have a full homologous series, (a) Shublik A source rock Prudhoe Bay Field long chain alkyl benzenes, (b) Shublik A long chain alkyl toluenes, (c) Kuparuk River Field oil stained core 3B-14 well long chain alkyl benzenes, (d) 3B-14 long chain alkyl toluenes. Numbers designate carbon numbers p is phytanyl-substituted aromatic asterisk designates background fragment peaks. Note, toluenes have ortho, meta and para isomers for each carbon number.

Fig. 12. Long chain alkyl toluenes (mjz = 106) also show variable depletions, (e) SWC-43, (f) SWC-31,...

The lone-pair electron on the nitrogen is responsible for electrophilic reactions on its side. Thus, heterocyclic nitrogen atom of quinoline and isoquinolines react with electrophiles, as alkyl halides, alkyl sulfates, alkyl-toluene-p-sulfonates, etc., providing quinolinium and isoquinolinium salts. 

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