Isopropylbenzene, oxidation

Berendes, F., Sabarth, N., Avcrhoff, B., and Gottschalk, G., Construction and use of an ipb DNA module to generate Pseudomonas strains with constitutive trichloroethene and isopropylbenzene oxidation activity, Appl. Environ. Microbiol., 64, 2454-2462, 1998. 

Alkylation of benzene with propylene produces cumene (isopropylbenzene). Oxidation of cumene at about 110°C to modest conversions (c. 20%) gives the hydroperoxide, which on treatment with sulphuric acid at 70-80°C produces phenol and acetone in equimolar quantities (90-92% of theory). 

Obtained synthetically by one of the following processes fusion of sodium ben-zenesulphonate with NaOH to give sodium phenate hydrolysis of chlorobenzene by dilute NaOH at 400 C and 300atm. to give sodium phenate (Dow process) catalytic vapour-phase reaction of steam and chlorobenzene at 500°C (Raschig process) direct oxidation of cumene (isopropylbenzene) to the hydroperoxide, followed by acid cleavage lo propanone and phenol catalytic liquid-phase oxidation of toluene to benzoic acid and then phenol. Where the phenate is formed, phenol is liberated by acidification. 

The most widely used process for the production of phenol is the cumene process developed and Hcensed in the United States by AHiedSignal (formerly AHied Chemical Corp.). Benzene is alkylated with propylene to produce cumene (isopropylbenzene), which is oxidized by air over a catalyst to produce cumene hydroperoxide (CHP). With acid catalysis, CHP undergoes controUed decomposition to produce phenol and acetone a-methylstyrene and acetophenone are the by-products (12) (see Cumene Phenol). Other commercial processes for making phenol include the Raschig process, using chlorobenzene as the starting material, and the toluene process, via a benzoic acid intermediate. In the United States, 35-40% of the phenol produced is used for phenoHc resins. 

The best preparative results from autoxidation are encountered when only one relatively reactive hydrogen is available for abstraction. The oxidation of isopropylbenzene (cumene) is carried out on an industrial scale, with the ultimate products being acetone and phenol ... 

The last example is mediated by a monooxygenase that can be induced by benzene, toluene, and ethylbenzene, and also by xylenes and styrene. A plausibly analogous situation exists for strains of Pseudomonas sp. and Rhodococcus erythropolis that were obtained by enrichment with isopropylbenzene, and that could be shown to oxidize trichloroethene (Dabrock et al. 1992). In addition, one of the pseudomonads could oxidize 1,1-dichloroeth-ene, vinyl chloride, trichloroethane, and 1,2-dichloroethane. 

Ptlugmacher U, B Averhoff, G Gottschalk (1996) Cloning, sequencing, and expression of isopropylbenzene degradation genes from Pseudomonas sp, strain JRl identification of isopropylbenzene dioxygenase that mediates trichloroethene oxidation. Appl Environ Microbiol 62 3967-3977. 

Photolytic. Major products reported from the photooxidation of isopropylbenzene with nitrogen oxides include nitric acid and lienzaldehyde (Altshuller, 1983). A / -hexane solution containing isopropylbenzene and spread as a thin film (4 mm) on cold water (10 °C) was irradiated by a mercury medium pressure lamp. In 3 h, 22% of the applied isopropylbenzene photooxidized into a,a-dimethylbenzyl alcohol, 2-phenylpropionaldehyde, and allylbenzene (Moza and Feicht, 1989). 

Methylenebis(oxy) ]bis(2-chloroformaldehyde), see Bis (2-chloroethoxy) methane Methylene chlorobromide, see Bromochloromethane Methylene dichloride, see Methylene chloride Methylene dimethyl ether, see Methylal Methyl 2,2-divinyl ketone, see Mesityl oxide Methylene glycol, see Formaldehyde Methylene glycol dimethyl ether, see Methylal Methylene oxide, see Formaldehyde Methyl ethanoate, see Methyl acetate (1 -Methylethenyl)benzene, see a-Methylstyrene Methyl ethoxol, see Methyl cellosolve 1-Methylethylamine, see Isopropylamine (l-Methylethyl)benzene, see Isopropylbenzene Methylethyl carbinol, see sec-Bntyl alcohol Methyl ethylene oxide, see Propylene oxide ds-Methylethyl ethylene, see cis-2-Pentene frans-Methylethyl ethylene, see frans-2-Pentene Methyl ethyl ketone, see 2-Bntanone Methylethylmethane, see Butane... 

Primary and secondary alcohols are quantitatively oxidized by peroxydisulfate to the corresponding aldehydes and ketones. Thus benzyl alcohols give aldehydes, and in the presence of Ni(II) and ammonia they gives nitriles secondary alcohols give the corresponding ketones . Interestingly, isopropylbenzene reacts with acetates in the presence of peroxy disulfate/Fe(II) to give lactones (equation 18). ... 

Production of phenol and acetone is based on liquid-phase oxidation of isopropylbenzene. Synthetic fatty acids and fatty alcohols for producing surfactants, terephthalic, adipic, and acetic acids used in producing synthetic and artificial fibers, a variety of solvents for the petroleum and coatings industries—these and other important products are obtained by liquid-phase oxidation of organic compounds. Oxidation processes comprise many parallel and sequential macroscopic and unit (or very simple) stages. The active centers in oxidative chain reactions are various free radicals, differing in structure and in reactivity, so that the nomenclature of these labile particles is constantly changing as oxidation processes are clarified by the appearance in the reaction zone of products which are also involved in the complex mechanism of these chemical conversions. 

Alkylation. Friedel-Crafts alkylation (qv) of benzene with ethylene or propylene to produce ethylbenzene [100-41 -4], CgH10, or isopropylbenzene [98-82-8], C9H12 (cumene) is readily accomplished in the liquid or vapor phase with various catalysts such as BF3 (22), aluminum chloride, or supported polyphosphoric acid. The oldest method of alkylation employs the liquid-phase reaction of benzene with anhydrous aluminum chloride and ethylene (23). Ethylbenzene is produced commercially almost entirely for styrene manufacture. Cumene [98-82-8] is catalytically oxidized to cumene hydroperoxide, which is used to manufacture phenol and acetone. Benzene is also alkylated with C1Q—C20 linear alkenes to produce linear alkyl aromatics. Sulfonation of these compounds produces linear alkane sulfonates (LAS) which are used as biodegradable deteigents. 

Current commercial syntheses of benzenol involve oxidation of methyl-benzene or isopropylbenzene (Section 16-9E). Oxidation of isopropylbenzene is economically feasible for the production of benzenol because 2-propanone... 

The biodegradation of trichloroethylene is the most studied since this is probably the most widespread halogenated solvent contaminant. Several substrates drive ttichlorethylene co-oxidation, including methane, propane, propylene, toluene, isopropylbenzene, and ammonia (25). The enzymes that metabolize these substrates have subtly different selectivities with regard to the halogenated solvents, and to date none are capable of co-oxidizing carbon tetrachloride or tetrachloroethylene. Complete mineralization of these compounds can, however, be achieved by sequential anaerobic and aerobic process. Biorem edia tion. 

Cumene or isopropylbenzene, diisopropylbenzene, and secondary butyl-benzene, although produced in smaller quantities than some of the other petrochemical alkylates, are very important petroleum refining products. Cumene is further reacted by oxidation to form cumene hydroperoxide, which is converted to phenol and acetone it is produced by alkylating benzene with propylene catalyzed by either solid or liquid phosphoric acid. Secondary butylbenzene is made by alkylating benzene with normal butylene using the same catalysts. Diisopropylbenzene is made by reacting cumene with propylene over solid phosphoric acid or aluminum chloride catalyst. 

Cumene (isopropylbenzene) is made by Friedel-Crafts alkylation of benzene with propylene. Although cumene is a high-octane automotive fuel, almost all of the cumene produced is used to make phenol (C6H5OH) and acetone [(CH3)2CO]. Cumene is easily oxidized to the corresponding hydroperoxide, which is readily cleaved in dilute acid, to yield phenol and acetone. 

Oxidation of hydrocarbons with dioxygen is more facile when the C-H bond is activated through aromatic or vinylic groups adjacent to it. The homolytic C-H bond dissociation energy decreases from ca. 100 kcal mol-1 (alkyl C-H) to ca. 85 kcal mol-1 (allylic and benzylic C-H), which makes a number of autoxidation processes feasible. The relative oxidizability is further increased by the presence of alkyl substituents on the benzylic carbon (see Table 4.6). The autoxidation of isopropylbenzene (Hock process, Fig. 4.49) accounts for the majority of the world production of phenol [131] ... 

Most important is the cumene process with an 80-85% share worldwide cumene (isopropylbenzene obtained from alkylation of benzene with propylene) is oxidized to the corresponding hydroperoxide which is decomposed to a mixture of phenol and acetone. In Japan the second most important process for acetone production is the direct oxidation of propylene with a 12% share. 

Oxidation of aromatic systems containing alkyl side-chains results in the formation of a carboxylic acid, irrespective of the length of the side-chain. The usual oxidizing agents are potassium permanganate [potassium manganate(VII)] or chromic acid [chromium(VI) acid]. For example, 1,4-dimethylbenzene is oxidized to benzene-1,4-dicarboxylic acid (tereph-thalic acid, 9), an important building block for polyesters. The oxidation of isopropylbenzene (cumene) to phenol is an important industrial process and is discussed in Chapter 4. 

Most phenol nowadays is obtained from isopropylbenzene (cumene), which is oxidized by air in the cumene proces.s (Scheme 4.1). Acetone (propanone) is a valuable by-product of the process and this route is a major source of this important solvent. The formation of cumene hydroperoxide proceeds by a free radical chain reaction initiated by the ready generation of the tertiary benzylic cumyl radical, which is a further illustration of the ease of attack at the benzylic position, especially by radicals (see Chapter 3). 

Industrially, the majority of phenol is produced by the oxidation of isopropylbenzene (cumene). 

Carbonium ions can be generated at a variety of oxidation levels. The alkyl carbocation can be generated from alkyl halides by reaction with a Lewis acid (RCl + AICI3) or by protonation of alcohols or alkenes. The reaction of an alkyl halide and aluminium trichloride with an aromatic ring is known as the Friedel-Crafts alkylation. The order of stability of a carbocation is tertiary > secondary > primary. Since many alkylation processes are slower than rearrangements, a secondary or tertiary carbocation may be formed before aromatic substitution occurs. Alkylation of benzene with 1-chloropropane in the presence of aluminium trichloride at 35 °C for 5 hours gave a 2 3 mixture of n- and isopropylbenzene (Scheme 4.5). Since the alkylbenzenes such as toluene and the xylenes (dimethylbenzenes) are more electron rich than benzene itself, it is difficult to prevent polysubsiitution and consequently mixtures of polyalkylated benzenes may be obtained. On the other hand, nitro compounds are sufficiently deactivated for the reaction to be unsuccessful. 

On an industrial scale, phenol is obtained by the oxidation of isopropylbenzene (cumene). Initially a hydroperoxide is formed, which then undergoes a fragmentation and rearrangement. The initial oxidation illustrates the susceptibility of benzylic positions to oxidative, particularly radical, attack (Scheme 4.14). 

Such reactions take place with p-xylene [28], ethylbenzene [28], and especially readily with isopropylbenzene (cumene) [29], where the intermediate free radical is stabilized not only by the aromatic ring but also by the two adjacent methyl groups. The oxidation of cumene to cumyl hydroperoxide (equation 162) followed by acid treatment is a basis for the large-scale production of phenol. 

Ethylbenzene and isopropylbenzene give 80 and 75%, respectively, of benzoic acid on oxidation with 15% nitric acid at higher temperatures [462]. The disadvantages of oxidations with nitric acid are the formation of nitrated byproducts (up to 12% of nitrobenzoic acid in the oxidation of ethylbenzene) and the necessity of working in glass-lined or stainless steel autoclaves [462]. 

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