4-Chlorobenzene reaction reduction

The only oxidation product of any significance was chlorobenzene (<1% of the benzene gave biphenyl), and during the course of a reaction not all the benzene lost could be accounted for as chlorobenzene formed. Reduction of the reaction mixture with hydrazine hydrate gave... 

Various Cu-exchanged zeolites have been examined in the nucleophilic substitution of bromo- and chlorobenzene towards aminated and oxygenated compounds (ref. 30). In amination a consecutive reaction to diphenylamine and reduction to benzene are the side-reactions (Fig. 10). 

The cyanobacteria Anflfcflenfl sp. strain PCC 7120 andNostoc ellipsosporum dechlorinated y-hexachloro[flflfleee]cyclohexane in the light in presence of nitrate to y-pentachlorocyclo-hexene (Figure 2.5), and to a mixture of chlorobenzenes (Kuritz and Wolk 1995). The reaction is dependent on the functioning of the nir operon involved in nitrite reduction (Kuritz et al. 1997). 

Hydrodehalogenations of chloro-, bromo-, and iodobenzene were carried out individually as well as in competitive reactions. When the reactions were carried out separately, the reduction of chlorobenzene closely paralleled that of bromobenzene, whereas the reduction of iodobenzene was slower. When they were allowed to react competitively, the reduction was highly selective, and the reaction was delayed, but iodobenzene reacted first followed by bromobenzene and then chlorobenzene. 

In the case of cobalt ions, the inverse reaction of Co111 reduction with hydroperoxide occurs also rather rapidly (see Table 10.3). The efficiency of redox catalysis is especially pronounced if we compare the rates of thermal homolysis of hydroperoxide with the rates of its decomposition in the presence of ions, for example, cobalt decomposes 1,1-dimethylethyl hydroperoxide in a chlorobenzene solution with the rate constant kd = 3.6 x 1012exp(—138.0/ RT) = 9.0 x 10—13 s—1 (293 K). The catalytic decay of hydroperoxide with the concentration [Co2+] = 10 4M occurs with the effective rate constant Vff=VA[Co2+] = 2.2 x 10 6 s— thus, the specific decomposition rates differ by six orders of magnitude, and this difference can be increased by increasing the catalyst concentration. The kinetic difference between the homolysis of the O—O bond and redox decomposition of ROOH is reasoned by the... 

In a water/chlorobenzene biphasic system, reduction of aromatic aldehydes by hydrogen transfer from aqueous sodium formate catalyzed by [ RuCl2(TPPMS)2 2] provided unsaturated alcohols exclusively (Scheme 10.7). Addition of 3-CD shghtly inhibited the reaction [13]. It was speculated that this inhibition was probably due to complexation of the catalyst by inclusion of one of the non-sulfonated phenyl rings of the TPPMS ligand, however, no evidence was offered. 

Nitro compounds in presence of carbonyl group are selectively reduced to amines in the presence of Raney nickel catalyst. Hydrazine reduces nitrdes yielding hydrazones. Under controlled reaction conditions other functional groups, including nitroso and oxime, may be reduced. Many partially hydrogenated derivatives, such as azo-, hydrazo-, and azoxy compounds may be obtained by partial reduction with hydrazine. Reaction with chlorobenzene yields benzene. 

After the solvent is added, the septum is replaced with a reflux condenser, topped with an N2-CO gas outlet, which is connected to a mineral oil bubbler. The reaction mixture is stirred at reflux for 12 h, and a slow N2 purge is maintained throughout this period. After cooling to room temperature, the gray-green powder is isolated by filtration, washed with 2 x 50 mL of fresh chlorobenzene, followed by 4 x 50 mL of hexane, and dried in vacuo (10 storr, 25 °C, 8h). It is important to free the product of all traces of chlorobenzene in order to obtain clean reductions in the following syntheses. Yield 47 g (or 96% based on WC16). 

Iron(II) chloride and bromide may be obtained from the reaction of the metal with the appropriate hydrogen halide at elevated temperatures.1 The chloride has also been made by the reduction of iron(III) chloride with hydrogen,1 from iron(III) chloride and the metal in tetrahydrofuran,2 and by the reaction of iron(III) chloride with chlorobenzene.3 The iodide has been prepared from the metal and iodine in a sealed tube at elevated temperatures.1... 

Benzoylchloride presents a special case since its presence completely stops the decarbonylation of benzaldehyde and no chlorobenzene is produced. Analysis of this reaction has shown that PhCOCl reacts with [Rh(dppp)2]Cl to produce Rh(Cl)2(PhCO)(dppp). This rhodium(III) complex is inert to migration and reductive elimination and therefore no decarbonylation products are produced (26). 

The intramolecular photoinduced electron transfer reaction of N-(o-chlorobenzyl)aniline 440 in the presence of sodium hydroxide in aqueous acetonitrile afforded, 9,10-dihydrophenanthridine and its dimer, which is reasonably explained by dechlorination from the radical anion of chlorobenzene chro-mophore followed by the cyclization (Scheme 130) [481], Similar photocyclization 9-(io-anilinoalkyl)-10-bromophenantherens 441 takes place to give spiro compounds, cyclized products, and reduction products dependent on the methylene chain length. The efficient intramolecular photocyclization occurs when the methylene tether is n = 3 [476] (Scheme 131). 

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