Chlorinated dichlorobenzenes

Continuous chlorination of benzene at 30—50°C in the presence of a Lewis acid typically yields 85% monochlorobenzene. Temperatures in the range of 150—190°C favor production of the dichlorobenzene products. The para isomer is produced in a ratio of 2—3 to 1 of the ortho isomer. Other methods of aromatic ring chlorination include use of a mixture of hydrogen chloride and air in the presence of a copper—salt catalyst, or sulfuryl chloride in the presence of aluminum chloride at ambient temperatures. Free-radical chlorination of toluene successively yields benzyl chloride, benzal chloride, and benzotrichloride. Related chlorination agents include sulfuryl chloride, tert-huty hypochlorite, and /V-ch1orosuccinimide which yield benzyl chloride under the influence of light, heat, or radical initiators. 

The chlorination of benzene can theoretically produce 12 different chlorobenzenes. With the exception of 1,3-dichlorobenzene, 1,3,5-trichlorobenzene, and 1,2,3,5-tetrachlorobenzene, all of the compounds are produced readily by chlorinating benzene in the presence of a Friedel-Crafts catalyst (see Friedel-CRAFTS reactions). The usual catalyst is ferric chloride either as such or generated in situ by exposing a large surface of iron to the Hquid being chlorinated. With the exception of hexachlorobenzene, each compound can be further chlorinated therefore, the finished product is always a mixture of chlorobenzenes. Refined products are obtained by distillation and crystallization. 

With the discontinuation of some herbicides, eg, 2,4,5-trichlorophenol [39399-44-5] based on the higher chlorinated benzenes, and DDT, based on monochlorobenzene, both for ecological reasons, the production of chlorinated benzenes has been reduced to just three with large-volume appHcations of (mono)chlorobenzene, o-dichlorobenzene, and -dichlorobenzene. Monochlorobenzene remains a large-volume product, considerably larger than the other chlorobenzenes, in spite of the reduction demanded by the discontinuation of DDT. 

The hquid-phase chlorination of benzene is an ideal example of a set of sequential reactions with varying rates from the single-chlorinated molecule to the completely chlorinated molecule containing six chlorines. Classical papers have modeled the chlorination of benzene through the dichlorobenzenes (14,15). A reactor system may be simulated with the relative rate equations and flow equation. The batch reactor gives the minimum ratio of... 

In the hquid-phase chlorination, 1,3-dichlorobenzene is found only in a small quantity, and 1,3,5-trichlorobenzene and 1,2,3,5-tetrachlorobenzene are undetectable. The ratios of 1,4- to 1,2-dichlorobenzene with various catalysts are shown in Table 3. Iodine plus antimony trichloride is effective in selectively chlorinating 1,2,4-trichlorobenzene to 1,2,4,5-tetrachlorobenzene (22), however, 1,2,4,5-tetrachlorobenzene is of limited commercial significance. 

Commercial chlorination of benzene today is carried out as a three-product process (monochlorobenzene and 0- and -dichlorobenzenes). The most economical operation is achieved with a typical product spHt of about 85% monochlorobenzene and a minimum of 15% dichlorobenzenes. Typically, about two parts of -dichlorobenzene are formed for each part of (9-isomer. It is not economical to eliminate the coproduction of the dichlorobenzenes. To maximize monochlorobenzene production (90% monochlorobenzene and 10% dichlorobenzene), benzene is lightly chlorinated the density of the reaction mixture is monitored to minimize polychlorobenzene production and the unreacted benzene is recycled. 

Dichlorobenzyl chloride (l,2-dichloro-4-chloromethylbenzene) containing some 2,3-dichlorobenzyl chloride is produced by the chloromethylation of o-dichlorobenzene ia oleum solution (73). Chlorination of 2-chloro-6-nitrotoluene at 160—185°C gives a mixture of 2,6-disubstituted benzal chloride and 2,6-dichlorobenzyl chloride (74). 

Ainino-3-chloroanthraquiQone [84-46-8] (68) is prepared from 2,3-dichloroanthraquiQone by partial chlorine replacement by a NH2 group. 2,3-Dichloroanthraquiaone [84-45-7] (67) is prepared by Friedel-Crafts reaction of phthaUc anhydride and 1,2-dichlorobenzene followed by ring closure of the resultant benzoylbenzoic acidia sulfuric acid (94). 

Today the sulphonation route is somewhat uneconomic and largely replaced by newer routes. Processes involving chlorination, such as the Raschig process, are used on a large scale commercially. A vapour phase reaction between benzene and hydrocholoric acid is carried out in the presence of catalysts such as an aluminium hydroxide-copper salt complex. Monochlorobenzene is formed and this is hydrolysed to phenol with water in the presence of catalysts at about 450°C, at the same time regenerating the hydrochloric acid. The phenol formed is extracted with benzene, separated from the latter by fractional distillation and purified by vacuum distillation. In recent years developments in this process have reduced the amount of by-product dichlorobenzene formed and also considerably increased the output rates. 

Organic chemicals made directly from chlorine include derivatives of methane methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene ortho- and para-dichlorobenzenes ethyl chloride, and ethylene chloride. 

Although limited to electron-rich aromatic compounds and alkenes, the Vilsmeier reaction is an important formylation method. When yV,A-dimethylformamide is used in excess, the use of an additional solvent is not necessary. In other cases toluene, dichlorobenzene or a chlorinated aliphatic hydrocarbon is used as solvent. ... 

Wilkes and co-workers have investigated the chlorination of benzene in both acidic and basic chloroaluminate(III) ionic liquids [66]. In the acidic ionic liquid [EMIM]C1/A1C13 (X(A1C13) > 0.5), the chlorination reaction initially gave chlorobenzene, which in turn reacted with a second molecule of chlorine to give dichlorobenzenes. In the basic ionic liquid, the reaction was more complex. In addition to the... 

Chlorination of benzene is an electrophilic substitution reaction in which CL serves as the electrophile. The reaction occurs in the presence of a Lewis acid catalyst such as FeCls. The products are a mixture of mono- and dichlorobenzenes. The ortho- and the para-dichlorobenzenes are more common than meta-dichlorobenzene. The ratio of the mono-chloro to dichloro products essentially depends on the benzene/chlorine ratio and the residence time. The ratio of the dichloro-isomers (0- to p- to m-dichlorobenzenes) mainly depends on the reaction temperature and residence time ... 

Typical liquid-phase reaction conditions for the chlorination of benzene using FeCls catalyst are 80-100°C and atmospheric pressure. When a high benzene/Cl2 ratio is used, the product mixture is approximately 80% monochlorobenzene, 15% p-dichlorobenzene and 5% o-dichlorobenzene. 

The symmetric series provides functional cyclohexadienes, whereas the non-symmetric one serves to build deuterated and/or functional arenes and tentacled compounds. In both series, several oxidation states can be used as precursors and provide different types of activation. The complexes bearing a number of valence, electrons over 18 react primarily by electron-transfer (ET). The ability of the sandwich structure to stabilize several oxidation states [21] also allows us to use them as ET reagents in stoichiometric and catalytic ET processes [18, 21, 22]. The last well-developed type of reactions is the nucleophilic substitution of one or two chlorine atoms in the FeCp+ complexes of mono- and o-dichlorobenzene. This chemistry is at least as rich as with the Cr(CO)3 activating group and more facile since FeCp+ activator is stronger than Cr(CO) 3. 

The mem-dichlorobenzene complex reacts with protected 0-aryltyrosines to give aryl ethers. Both chlorine atoms can be sequentially substituted to give symmetrical or disymmetrical triaryl diethers (Scheme XVI). The building up of such diaryl ethers from phenolic compounds which have amino groups in their side chains... 

Structural evidence Only one dichlorobenzene in which the two chlorine atoms are attached to adjacent carbon atoms exists. 

If the Kekule structure were correct, there would be two distinct dichlorobenzenes in which the chlorine atoms are attached to adjacent carbon atoms (13), one in which the carbon atoms are joined by a single bond and one with a double bond. In fact, only one such compound is known. 

There are three different dichlorobenzenes, CgH4Cl2, which differ in the relative positions of the chlorine atoms on the benzene ring, (a) Which of the three forms are polar ... 

Octachlorodibenzo- -dioxin. Pentachlorophenol was purified by sublimation and recrystallization to yield a product with the following composition trichlorophenol, 0.04% tetrachlorophenol, 0.07% and pentachlorophenol, 100.4 1%. Pentachlorophenol (300 grams, 1.13 mole) was dissolved in 900 ml of trichlorobenzene and chlorinated anhydrously for 18 hours at reflux. Ghlorine addition was stopped and the mixture was heated for 28 more hours at reflux. The crystalline product was washed with 2-liter portions of chloroform, IN NaOH, methanol, and water. Analysis by GLG suggested the presence of 5-15% heptachloro-dibenzo-p-dioxin. The mixture was carefully added to a cleaning solution of 200 ml water, 3.5 liters sulfuric acid, and 125 grams sodium dichromate. The mixture was heated at 150 °G for six hours. The product was recrystallized from hot o-dichlorobenzene and then from anisole. The purified product (160 grams, mp 329.8° 0.5°G) contained <0.1% heptachlorodibenzo-p-dioxin, determined by GLG. 

Mutations at the active site of CYPlOl (cytochrome P450j,j jj) from a strain of Pseudomonas putida made possible the monooxygenation of chlorinated benzenes with less than three substituents to chlorophenols, with concomitant NIH shifts for 1,3-dichlorobenzene (Jones et al. 2001). Further mutations made it possible to oxidize even pentachlorobenzene and hexachlorobenzene to pentachlorophenol (Chen et al. 2002). Integration of the genes encoding cytochrome PTSO. into Sphingobium chlorophenolicum enabled this strain to partially transform hexachlorobenzene to pentachlorophenol (Yan et al. 2006). 

Attention has been directed to the dechlorination of polychlorinated benzenes by strains that use them as an energy source by dehalorespiration. Investigations using Dahalococcoides sp. strain CBDBl have shown its ability to dechlorinate congeners with three or more chlorine substituents (Holscher et al. 2003). Although there are minor pathways, the major one for hexachlorobenzene was successive reductive dechlorination to pentachlorobenzene, 1,2,4,5-tetrachlorobenzene, 1,2,4-trichlorobenzene, and 1,4-dichlorobenzene (Jayachandran et al. 2003). The electron transport system has been examined by the use of specific inhibitors. lonophores had no effect on dechlorination, whereas the ATP-synthase inhibitor A,A -dicyclohexylcarbodiimide (DCCD) was strongly inhibitory (Jayachandran et al. 2004). 

Monochlorobenzene is produced by the reaction of benzene with chlorine. A mixture of monochlorobenzene and dichlorobenzene is produced, with a small amount of trichlorobenzene. Hydrogen chloride is produced as a byproduct. Benzene is fed to the reactor in excess to promote the production of monochlorobenzene. 

Design a plant to produce 20,000 tonnes/year of monochlorobenzene together with not less than 2000 tonnes/year of dichlorobenzene, by the direct chlorination of benzene. 

What about dichlorobenzenes Substitution of another hydrogen by chlorine creates another local dipole and a more polar molecule. Certainly 1,2 and 1,3-dichlorobenzene are more polar but 1,4-dichlorobenzene poses a quandary. It is what chemist call a polar molecule but the opposing chlorines result in a net molecular dipole of zero. Right Perhaps it is best for chemists to think in terms of bond-dipoles rather than molecular dipoles and in many cases this is the case in chemical separation discussions. (Reader should look up the properties of the dichlorobenzenes, such as melting and boiling point and liquid density.)... 

Chlorinated hydrocarbons that have been determined in extracts of river sediments by gas chromatography include higher chlorinated aromatic hydrocarbons, alpha and gamma hexachlorocyclohexanes and dichlorobenzenes in amounts down to 0.5pg kg 1 in the sediment [28-30]. 

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