Chlorobenzene from benzene

Manufacture of Phenol by Regenerative Process. The regenerative, or Raschig, process for the production of phenol is based on a combination of two well-known processes (1) the production of chlorobenzene from benzene and hydrogen chloride and air (see Chap. 6) and (2) the hydrolysis of chlorobenzene with water vapor in the presence of a catalyst. ... 

How would the reaction conditions differ from those in part b i if you wanted to make chlorobenzene from benzene and chlorine ... 

The relative rate is derived from the kinetic data " by stepwise comparison with m-nicrotoluene, chlorobenzene and benzene. Kinetic data are available for the acidity range 8o-o-Q5-6 % sulphuric acid. See also ref. 43. 

A Methylamino)phenol. This derivative, also named 4-hydroxy-/V-methy1ani1ine (19), forms needles from benzene which are slightly soluble in ethanol andinsoluble in diethyl ether. Industrial synthesis involves decarboxylation of A/-(4-hydroxyphenyl)glycine [122-87-2] at elevated temperature in such solvents as chlorobenzene—cyclohexanone (184,185). It also can be prepared by the methylation of 4-aminophenol, or from methylamiae [74-89-5] by heating with 4-chlorophenol [106-48-9] and copper sulfate at 135°C in aqueous solution, or with hydroquinone [123-31 -9] 2l. 200—250°C in alcohoHc solution (186). 

A mixture of 2-chloro-A-(2-hydroxyl-l-methyl-2-phenylethyl)benzamide (44) (9.5g, 24.9 mmol) and P2O5 in o-chlorobenzene (1,50 mL) was refluxed overnight. Upon completion, the reaction was cooled to room temperature and then chilled to 0 °C. To the crude reaction mixture, 300 mL of water was cautiously added. The resulting dark solution was washed with toluene (2 x 50 mL). The aqueous layer was cooled to 0 °C and 50% NaOH added to final pH of 11. The resulting mixture was extracted with toluene (4 x 50 mL). The toluene fractions were combined, dried, filtered and concentrated in vacuo. The residue was crystallized from benzene to afford l-(2-chlorophenyl)-3-methylisoquinoline (45) as a white solid (6.68g, 80%). M.P. = 107-108 °C H NMR (CDCI3) S 8.45 (s, IH), 8.11 (d, IH), 7.85 (dt, IH), 7.41-7.68 (bm, 6H), 2.51 (s, 3H). 

From this work a relative reactivity for chlorobenzene to benzene of 0.065 is obtained and this may be compared with a value of 0.34 obtained by Kilpatrick and Meyer163 for bromobenzene at 12.3 °C this is rather a large difference in view of the fact that there is very little ortho sulphonation of either substrate. 

Stock and Baker2 5 9 measured the relative rates of chlorination of a number of halogenated aromatics in acetic acid containing 20.8 M H20 and 1.2 M HC1 at 25 °C and the values of the second-order rate coefficients (103Ar2) are as follows p-xylene (11,450), benzene (4.98), fluorobenzene (3.68), chlorobenzene (0.489), bromobenzene (0.362), 2-chlorotoluene (3.43), 3-chlorotoluene (191), 4-chloro-toluene (2.47), 4-fluorotoluene (9.70), 4-bromotoluene (2.47). Increasing the concentration of the aromatic, however, caused, in some cases, a decrease in the rate coefficients thus an increase in the concentration of chlorobenzene from 0.1 M to 0.2 M caused a 20 % decrease in rate coefficient, whereas with 4-chloro-and 4-bromo-toluene, no such change was observed. 

Oxidation of benzene (and also chlorobenzene and toluene) by Mn(III) acetate in glacial acetic acid gives a mixture of products including benzyl acetate (from benzene) indicating an initial attack on the aromatic by CH2C02H . The kinetics and actual rate of disappearance of Mn(III) are the same for CgHs and... 

Chlorobenzene(s), 3 602 6 211-225 24 275 Antoine constants, 6 215t from benzene, 3 619t, 620 chlorocarbon/chlorohydrocarbon of industrial importance, 6 227t diffusion coefficient in air at 0° C, l 70t economic aspects, 6 219-222 health and safety factors, 6 218-219 manufacture, 6 213-217 physical and thermodynamic properties, 6 214t... 

There is a long history of the preparation of explosive solids or oils from interaction of diazonium salts with solutions of various sulfides and related derivatives. Such products have arisen from benzene- and toluene-diazonium salts with hydrogen, ammonium, or sodium sulfides [1,5] 2- or 3-chlorobenzene-, 4-chloro-2-methylbenzene-, 2- or 4-nitrobenzene- or 1- or 2-naphthalene-diazonium solutions with hydrogen sulfide, sodium hydrogen sulfide or sodium mono-, di- or poly-sulfides [l]-[4,7], 4-Bromobenzenediazonium solutions gave with hydrogen sulfide at -5°C a product which exploded under water at 0°C [2], and every addition of a drop of 3-chlorobenzenediazonium solution to sodium disulfide solution... 

Fig. 1. First overtone band of the surface OH-groups of alumosilicagel, immersed into carbon tetrachloride (1), chlorobenzene (2), benzene (3), toluene (4) and acetone (5). (From top to bottom)...

Chlorobenzene is used m the production nt phenol, ont line, biphenyl, polychlorobcnzcne. and DOT It is produced from benzene by chlorine substtlalion or oxychlnrination. 

In the chlorobenzene process, benzene is chlorinated at 38 to 60°C in the presence of ferric chloride (FeCl3) catalyst. The chlorobenzene is hydrolyzed with caustic soda at 400°C and 11,000 psi (2.56 kPa) to form sodium phen-ate. The impure sodium phenate reacts with hydrochloric acid to release the phenol from the sodium salt. 

Other impurities which may be present in chlorodinitrobenzene are chloro-nitrobenezenes, as products of an incomplete nitration, m- dinitrobenzene formed from benzene present in the chlorobenzene Mid chloropicrin. 

Hydrolysis of chlorobenzene and the influence of silica gel catalysts on this reaction have been studied by Freidlin and co-workers (109). Pure silica gel gave up to 45% phenol from chlorobenzene at 600°C. When the silica gel was promoted with 2% cupric chloride, up to 75% phenol was obtained (381). A number of other salts were tested by Freidlin and co-workers as promoters, but they exerted an adverse effect on the activity or selectivity of the catalyst. With 0.2% cupric chloride and 6% metallic copper, the activity of silica-gel was doubled (389). At 500° under the above conditions, the halides were hydrolyzed at rates decreasing in the following order chloride, bromide, iodide, fluoride (110). The specific activation of aryl halides by cupric chloride was demonstrated by conversion of chlorobenzene to benzene and of naphthyl chloride to naphthalene when this catalyst was supported on oxides of titanium or tin (111). The silica promoted with cupric chloride was also found to be suitable for hydrolysis of chlorophenols and dichlorobenzenes however, side reactions were too prominent in these cases (112). 

Suggest syntheses for each of the following compounds IVoiii the starting material indicated (a) 3-bromoaniline from benzene (b) 3-nitrobenzoic acid from toluene c) 4-nilrobenzoic acid from toluene (d) 4-mclhyibenzoplicnoiiic from benzoic acid (c) 1-nieihoxy-2.4-dinitrobenzene from chlorobenzene. 

Derivation From chlorobenzene Grignard reagent and methyltrichlorosilane or from benzene and me-thyldichlorosilane. 

This system has been cited frequently (e.g. [96]) as a method for the production of aromatic acids. Hence, benzoic acid is formed from the hydroiysis of benzoyl chloride, prepared from benzene and an excess of liquid phosgene in the presence of dissolved aluminium(III) chloride [1754]. Toluene or chlorobenzene react similarly to give 4-chloro- or 4-methyIbenzoic acids via the corresponding acid chlorides. 

There have been notable shifts in raw materials for the manufacture of maleic anhydride and phenol. Made for many years by the oxidation of benzene, maleic anhydride now is made by a catalytic process from butane. The butane process was found to result in lower costs of operation as well as reduced environmental, safety, and health hazards. Another example is the manufacture of phenol, initially made from benzene or chlorobenzene. Subsequently, however, with large supplies of cumene from the catalytic reaction of benzene and propylene, production came to be dominated by cumene-derived phenol, which, requires a lower capital investment and offers reduced operating expenses as well as reduced environmental and safety problems. A novel... 

Biotransformation of chlorobenzene by P. putida grown on toluene or benzene resulted in the formation of 3-chlorocatechol this inhibited further metabolism by catechol 2,3-dioxygenase, so that its presence resulted in the formation of catechols even from benzene and toluene (Gibson et al. 1968 Klecka and Gibson 1981 Bartels et al. 1984). The same situation has emerged in the degradation of 3-chlorobenzoate the inhibition that would result from... 

The reaction mixture was allowed to warm gradually to 50°C. The reaction was quenched by pouring into ice water. The aqueous suspension was heated to hydrolyze p-chlorobenzenesulfonyl chloride (II) to the water-soluble sulfonic acid. The desired product was filtered and washed with water until essentially neutral. Bis (4-chlorophenyl) sulfone was purified by recrystallization from benzene—m.p. 145°-147°C (4). Extremely low yields were obtained by this process. By contrast, yields in excess of 90% have been reported in processes that involve the reaction of chlorobenzene with sulfur trioxide and dimethyl or diethyl sulfate (5, 6). 

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