Cumene nitration

Use Solvent xylene cumene nitrated, for incorporation in dynamite. 

Copper(II) sulfate Cumene hydroperoxide Cyanides Cyclohexanol Cyclohexanone Decaborane-14 Diazomethane 1,1-Dichloroethylene Dimethylformamide Hydroxylamine, magnesium Acids (inorganic or organic) Acids, water or steam, fluorine, magnesium, nitric acid and nitrates, nitrites Oxidants Hydrogen peroxide, nitric acid Dimethyl sulfoxide, ethers, halocarbons Alkali metals, calcium sulfate Air, chlorotrifluoroethylene, ozone, perchloryl fluoride Halocarbons, inorganic and organic nitrates, bromine, chromium(VI) oxide, aluminum trimethyl, phosphorus trioxide... 

From the recent advances the heteroatom-carbon bond formation should be mentioned. As for the other reactions in Chapter 13 the amount of literature produced in less than a decade is overwhelming. Widespread attention has been paid to the formation of carbon-to-nitrogen bonds, carbon-to-oxygen bonds, and carbon-to-sulfur bonds [29], The thermodynamic driving force is smaller in this instance, but excellent conversions have been achieved. Classically, the introduction of amines in aromatics involves nitration, reduction, and alkylation. Nitration can be dangerous and is not environmentally friendly. Phenols are produced via sulfonation and reaction of the sulfonates with alkali hydroxide, or via oxidation of cumene, with acetone as the byproduct. 

The important derivatives of benzene are shown in Table 8.8. Ethylbenzene is made from ethylene and benzene and then dehydrogenated to styrene, which is polymerized for various plastics applications. Cumene is manufactured from propylene and benzene and then made into phenol and acetone. Cyclohexane, a starting material for some nylon, is made by hydrogenation of benzene. Nitration of benzene followed by reduction gives... 

Materials. Chemically pure solvents and reagent grade ceric ammonium nitrate were used as received. Cumene hydroperoxide was purified via the sodium salt. Lucidol tert-butyl hydroperoxide was purified by low temperature crystallization. Tetralin hydroperoxide, cyclohexenyl hydroperoxide, and 2-phenylbutyl-2-hydroperoxide were prepared by hydrocarbon oxidation and purified by the usual means. 1,1-Diphenyl-ethyl hydroperoxide and triphenylmethyl hydroperoxide were prepared from the alcohols by the acid-catalyzed reaction with hydrogen peroxide (10). 

Synonym Gamma-Chloropropylene Oxide 3-Chloro-1,2-Propylene Oxide Chlorosulfonic Acid Chlorothene Chiorotoluene, Alpha Alpha-Chlorotoluene Omega-Chlorotoluene Chlorotrifluoroethylene Chlorotrimethylsilane Chlorsulfonic Acid Clilorylen Clip Chromic Acid Chromic Anhydride Chromic Oxide Chromium (VI) Dioxychloride Chromium Oxychloride Chromium Trioxide Chromyl Chloride Cianurina Citric Acid Citric Acid, Diammonium Salt Clarified Oil Clorox Cc Ral Coal Tar Oil Cobalt Acetate Cobalt Acetate Tetrahydrate Cobalt (II) Acetate Cobalt Chloride Cobalt (II) Chloride Cobaltous Acetate Cobaltous Chloride Cobaltous Chloride Dihydrate Cobaltous Chloride Hexahydrate Cobaltous Nitrate Cobaltous Nitrate Hexahydrate Cobaltous Sulfate Heptahydrate Cobalt Nitrate Cobalt (II) Nitrate Cobalt Sulfate Compound Name Epichlorohydrin Epichlorohydrin Chlorosulfonic Acid Trichloroethane Benzyl Chloride Benzyl Chloride Benzyl Chloride Trifluorochloroethylene Trimethylchlorosilane Chlorosulfonic Acid Trichloroethylene Cumene Hydroperoxide Chromic Anhydride Chromic Anhydride Chromic Anhydride Chromyl Chloride Chromyl Chloride Chromic Anhydride Chromyl Chloride Mercuric Cyanide Citric Acid Ammonium Citrate Oil Clarified Sodium Hypochlorite Coumaphos Oil Coal Tar Cobalt Acetate Cobalt Acetate Cobalt Acetate Cobalt Chloride Cobalt Chloride Cobalt Acetate Cobalt Chloride Cobalt Chloride Cobalt Chloride Cobalt Nitrate Cobalt Nitrate Cobalt Sulfate Cobalt Nitrate Cobalt Nitrate Cobalt Sulfate... 

Cumene Hydroperoxide Copper Acetate Copper Arsenite Copper Bromide Copper Chloride Copper Fluoioborate Copper Arsenite Copper Cyanide Copper Nitrate Copper Oxalate Copper Sulfate... 

Direct nitration of the prescribed starting material cumene (isopropylbenzene) is not suitable, because isopropyl is an ortho, para-directing substituent and will give the target molecule... 

The charge to the unit is treated refinery propane-propylene along with recycle benzene from the recycle column overhead. Make-up benzene is added to the recycle. Nitration-grade benzene is usually used so that a drag stream of benzene is not required to remove contaminants from the unit. Table IX shows the component analysis of the various streams in the cumene process. 

Difficulties met in separating chemical individuals from higher fractions of light oil and lower fractions of middle oil stimulated attempts at the direct nitration of solvent-naphtha, the name given to a mixture of isomers comprising xylenes, ethylbenzene, pseudo-cumene (1,2,4-trimethylbenzene), ethyltoluene and mesitylene. 

It is generally admitted that skeletal transformations of hydrocarbons are catalyzed by protonic sites only. Indeed good correlations were obtained between the concentration of Bronsted acid sites and the rate of various reactions, e g. cumene dealkylation, xylene isomerization, toluene and ethylbenzene disproportionation and n-hexane cracking10 12 On the other hand, it was never demonstrated that isolated Lewis acid sites could be active for these reactions. However, it is well known that Lewis acid sites located in the vicinity of protonic sites can increase the strength (hence the activity) of these latter sites, this effect being comparable to the one observed in the formation of superacid solutions. Protonic sites are also active for non skeletal transformations of hydrocarbons e g. cis trans and double bond shift isomerization of alkenes and for many transformations of functional compounds e.g. rearrangement of functionalized saturated systems, of arenes, electrophilic substitution of arenes and heteroarenes (alkylation, acylation, nitration, etc ), hydration and dehydration etc. However, many of these transformations are more complex with simultaneously reactions on the acid and on the base sites of the solid... 

Mononitration of benzene is carried out at about 60° and dinitration meta isomer) at about 95° further nitration is difficult. In a similar manner, toluene gives rise to o- and p-nitrotoluenes (90%) and a small quantity of the meta isomer, isopropylbenzene (cumene) goes predominantly to p-nitrocumene (89%), and t-butylbenzene to p-nitro-t-butyl-benzene (74%). For the nitration of an easily oxidizable substance like p-cymene, a good emulsion and careful temperature control are important. ... 

The 50 largest-volume chemicals contain many derived from fossil carbon sources. Their 1995 volumes in billions of pounds produced in the United States4 are ethylene (46.97), ammonia (35.60), propylene (25.69), methyl tert-butyl ether (17.62), ethylene dichloride (17.26), nitric acid (17.24), ammonium nitrate (15.99), benzene (15.97), urea (15.59), vinyl chloride (14.98), ethylbenzene (13.66), styrene (11.39), methanol (11.29), carbon dioxide (10.89), xylene (9.37), formaldehyde (8.11), terephthalic acid (7.95), ethylene oxide (7.62), toluene (6.73), p-xylene (6.34), cumene (5.63), ethylene glycol (5.23), acetic acid... 

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