Tert-Butyl benzene

In an alternative procedure 26 g. of anhydrous ferric chloride replace the aluniiniuni chloride, the mixture is cooled to 10°, and the 50 g. of tert.-butyl chloride is added. The mixture is slowly warmed to 25° and maintained at this temperature until no more hydrogen chloride is evolved. The reaction mixture is then washed with dilute hydrochloric acid and with water, dried and fractionally distilled. The yield of tert.-butyl benzene, b.p. 167- 170°, is 60 g. 

Figure 12 7 illustrates attack on the benzene ring by tert butyl cation (step 1) and subsequent formation of tert butylbenzene by loss of a proton from the cyclohexadienyl cation intermediate (step 2)... 

Step 1 Once generated by the reaction of tert butyl chloride and aluminum chloride tert butyl cation attacks the TT electrons of benzene and a carbon-carbon bond is formed... 

Ethereal methyl1ithiurn (as the lithium bromide complex) was obtained by the submitters from Aldrich Chemical Company Inc. The checkers used 1.19 M methyl1ithiurn-lithium bromide complex in ether supplied by Alfa Products, Morton/Thiokol, Inc. The concentration of the methyllithium was determined by titration with 1.0 M tert-butyl alcohol in benzene using 1,10-phenanthroline as indicator. The submitters report that ethereal methyllithium of low halide content purchased from Alfa Products, Morton/Thiokol, Inc., gave similar results. 

Di-tert-butyl-p-cresol (2,6-di-tert-butyl-4-methylphenol, butylatedhydroxytoluene, BHT) [128-37-0] M 230.4, m 71.5 , pK 12.23. Dissolved in n-hexane at room temperature, then cooled with rapid stirring, to -60°. The ppte was separated, redissolved in hexane, and the process was repeated until the mother liquor was no longer coloured. The final product was stored under N2 at 0° [Blanchard J Am Chem Soc 82 2014 7960]. Also crystd from EtOH, MeOH, benzene, n-hexane, methylcyclohexane or pet ether (b 60-80°), and dried under vacuum. 

Stage 1 Preparation of 2-Phenyl-2-Methoxy-Ethyl Bromide - 1.3 mols of tert-butyl hypo-bromite is added slowly and with agitation to a mixture of 107 grams (1 mol) of vinyi-benzene (styrene) and 250 mi of methanol (99%), kept at -10°C. When the addition of the reactant is finished, the mixture is allowed to return to ambient temperature, it is washed in water and dried on anhydrous NajS04. Rectification is effected in vacuo in order to obtain a colorless liquid BP,j = 113°C, BPj.j = 84°C, = 1,5429, yield = 76%. 

A) The preparation of [H-chloroethoxyjchloromethyl]phosphonic acid Acetaldehyde (1.1 mol) and hydroxymethylphosphonlc acid (1 mol) in 500 ml of benzene are saturated with hydrogen chloride gas at 10°C to 15°C. The mixture is aged at 25°C for 24 hr, the solvent distilled out in vacuo and the residue flushed three times with benzene to remove all traces of hydrogen chloride. The residue is taken up in benzene (500 ml), treated with tert-butyl hypochlorite (0.8 mol) and azobisisobutyronitrile (0.8 mm) at 40°C until titration shows the absence of hypochlorite and the solution is then evaporated to yield [(1-chloro-ethoxy)chloromethyll phosphonic acid in the form of an oil. 

The mechanism of side-chain oxidation is complex and involves reaction of C-J-l bonds at the position next to the aromatic ring to form intermediate ben-zylic radicals, tert- Butyl benzene has no benzylic hydrogens, however, and is therefore inert. 

The configuration of the adduct with dimethyl acetylenedicarboxylate depends on the nature of the solvent used protic solvents, such as methanol or ethanol (but not tert-butyl alcohol), favor formation of (Z)-25a, whereas in nonprotic solvents, such as benzene, chloroform or acetonitrile, ( )-25a is the major product. 

Groundwater contaminant plumes from accidental gasoline releases often contain methyl-tert-butyl ether. Experiments with certain soil microorganisms showed that a culture able to degrade methyl-tert-butyl ether did not degrade benzene and toluene. Further interactions were observed [468]. 

R. A. Deeb, H. Y. Hu, J. R. Hanson, K. M. Scow, and L. Alvarez-Cohen. Substrate interactions in BTEX [benzene, toluene, ethylbenzene, and xylene] and MTBE [methyl tert-butyl ether] mixtures by an MTBE-degrading isolate. Environ Sci Technol, 35(2) 312-317, 2001. 

The United States Environmental Protection Agency (U.S. EPA) has identified several hundred MTBE-contaminated sites that have performed treatment of soil and groundwater to remove or destroy MTBE.1 Many of these sites have also treated other fuel components, primarily benzene, toluene, ethylbenzene, and xylene (BTEX), and some have treated fuel oxygenates other than MTBE. Although others have reported about treatment technologies for MTBE cleanup,2 only limited information has been published about cleanup of other oxygenates. These oxygenates include ether compounds, such as ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), diisopropyl ether (DIPE), and tert-amyl ethyl ether (TAEE), as well as alcohol compounds, such as tert-butyl alcohol (TBA), tert-amyl alcohol (TAA), ethanol, and methanol. 

A quantitative evaluation of the acid properties is quite difficult. One example is nevertheless quite instructive in l,3-di-tert-butyl-2,2-dimethyl-1,3,2,4L2-diazasila-stannetidine (1) the tin atom can be replaced by the much smaller aluminium-methyl group 124). While / is monomeric in benzene, 36 is dimeric ... 

The cyclic diazastannylene 1 has been found to be very suitable for this type of reaction 1S5) (cf. also Sect. 4.1). In Eqs. (43) and (44) the chlorine atoms of the Lewis acids are transferred to the divalent tin atom resulting in the formation of 57 and 76 and tin(II) chloride, the latter being insoluble in benzene. In (45) the solubility of the produced compounds is again important because SnS precipitates from the solution thus, the equilibrium is shifted to the right (in Eqs. (43)-(45) R denotes tert-butyl). 

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