Chlorobenzene, alkylation

The next and only other major kinetic study was carried out by Jensen and Brown184, who used aluminium chloride as catalyst, nitrobenzene as solvent, benzene- and p-toluene-sulphonyl chlorides as sulphonylating agents and benzene, chlorobenzene, alkyl- and polyalkylbenzenes as aromatic substrates184. 

Alkaline hydrolysis of a variety of organic compounds nitration of chlorobenzene alkylation of benzene with straight-chain olefins reduction of aromatic nitro compounds to corresponding aromatic amines with aqueous NajS or Na2Sj. 

Synthesis of other organic compounds, e.g. chlorobenzenes, alkyl chlorides (particularly methyl chloride for lead alkyls), herbicides (10)... 

Methyl iodide ethyl bromide ethyl iodide, higher alkyl halides, chloroform, iodoform, carbon tetrachloride, chlorobenzene, bromobenzene, iodobenzene, benzyl chloride (and nuclear substituted derivatives)... 

Because carbon is sp hybridized m chlorobenzene it is more electronegative than the sp hybridized carbon of chlorocyclohexane Consequently the withdrawal of electron density away from carbon by chlorine is less pronounced m aryl halides than m alkyl halides and the molecular dipole moment is smaller... 

PMMA is not affected by most inorganic solutions, mineral oils, animal oils, low concentrations of alcohols paraffins, olefins, amines, alkyl monohahdes and ahphatic hydrocarbons and higher esters, ie, >10 carbon atoms. However, PMMA is attacked by lower esters, eg, ethyl acetate, isopropyl acetate aromatic hydrocarbons, eg, benzene, toluene, xylene phenols, eg, cresol, carboHc acid aryl hahdes, eg, chlorobenzene, bromobenzene ahphatic acids, eg, butyric acid, acetic acid alkyl polyhaHdes, eg, ethylene dichloride, methylene chloride high concentrations of alcohols, eg, methanol, ethanol 2-propanol and high concentrations of alkahes and oxidizing agents. 

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. 

Tnfluoroacetic anhydnde in a mixture with sulfuric acid is an efficient reagent for the sulfonylation of aromatic compounds [44] The reaction of benzene with this system in nitromethane at room temperature gives diphenyl sulfone in 61% yield Alkyl and alkoxy benzenes under similar conditions form the corresponding diaryl sulfones in almost quantitative yield, whereas yields of sulfones from deactivated arenes such as chlorobenzene are substantially lower [44] The same reagent (tnfluoroacetic anhydride-sulfunc acid) reacts with adamantane and its derivatives with formation of isomeric adamantanols, adamantanones, and cyclic sultones [45]... 

The antifungal agent, dianithazole (76), is prepared by cleaving the ether function of 2-dimethylamino-6-ethoxybenzothia-zole (74) with aluminum chloride in chlorobenzene and then alkylating the sodium salt of the resulting phenol (75) with 2-diethylaminoethyl chloride. 

Fig. 13 Synthesis of oxazoles on JandaJel. Reagents and conditions a toluene, alkyl acetoacetate (R0(C0)CH2C0R R =t-Bu), reflux, 6h or alkyl acetoacetate (R = Me, Et), toluene, LiC104, reflux, 6h fc dodecylbenzenesulfonyl azide, EtsN, toluene, rt, 16 h c benzamide, Rh2(oct)4, toluene, 65 °C, Ih rf Burgess reagent, pyridine, chlorobenzene, MW 100 °C, 15 min (or 80 °C, 4 h with conventional heating) e AICI3, piperidine, CH2CI2, rt, 16 h...

The alkylation of benzene derivatives with methyl(vinyl)dichlorosilane (3) will be described in detail. Alkylation of monosubstituted benzenes such as toluene, chlorobenzene, and biphenyl at 75-80 C for 2 h afforded the corresponding alkylated products in 50-63% yields." ... 

The alkylation of benzenes having electron withdrawing groups, such as chlorobenzene and anisole, with 3 gave only monoalkylated, dialkylated. and trialkylated compounds.but no peralkylated products were obtained even upon heating of... 

Sulphated zirconia catalysts can be acidic or superacidic depending on the method of treatment. A variety of acid-catalysed reactions, referred to earlier in this section, can be carried out with sulphated zirconia. Yadav and Nair (1999) have given a state-of-the art review on this subject. Examples of benzylation of benzene with benzyl chloride / benzyl alcohol, alkylation of o-xylene with. styrene, alkylation of diphenyl oxide with 1-dodecene, isomerization of epoxides to aldehydes, acylation of benzene / chlorobenzene with p-chloro benzoylchloride, etc. are covered in the review. 

A variety of other reactions such as acylation of toluene, anisole, and chlorobenzene to give selectively p-isomer, alkylations, etc. have been conducted with IL. 

As indicated in Table 5.5, the addition of an inorganic salt appears to improve the yields of the A-alkylated hydrazobenzenes by a common ion effect. In the absence of the inorganic salt, the best yields in the shortest reaction times are attained when chlorobenzene is used as the organic phase. Stoichiometric amounts of the catalyst are used in this reaction and it is conceivable that either the solid liquid or the liquiddiquid two-phase conditions, with a catalytic amount of the ammonium salt, as used in the A-alkylation of the triazenes, may be a more effective process. 

Figure 3.3 SPMD-water partition coefficients (ml mL units) as a function of log Kqw for PAHs—filled circles Huckins et al. (1999), filled triangles Huckins et al. (2004) phenanthrene, PCB 52, and p,p -DDE—open triangles Huckins et al. (2002a) chlorobenzenes, PAHs, and PCBs—squares Booij et al. (2003a) pesticides—filled diamonds Sabaliunas and Sodergren (1997) and HCHs—open diamonds Vrana and Schiiurmann (2002). Additional kjw data were calculated for PCBs (asterisks) and alkylated benzenes (crosses) using the fCmw data from Lefkovitz et al. (1996) and Reynolds et al. (1990), and the data from Chiou (1985).

Spurred by our desire to avoid use of expensive dipolau aprotic solvents in nucleophilic aromatic substitution reactions, we have developed two alternative phase transfer systems, which operate in non-polar solvents such as toluene, chlorobenzene, or dichlorobenzene. Poleu polymers such as PEG are Inexpensive and stable, albeit somewhat inefficient PTC agents for these reactions. N-Alkyl-N, N -Dialkylaminopyridinium salts have been identified as very efficient PTC agents, which are about 100 times more stable to nucleophiles than Bu NBr. The bis-pyridinium salts of this family of catalysts are extremely effective for phase transfer of dianions such as bis-phenolates. 

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