Dibenzo-p-dioxin chlorination

Ryan, J.J., R. Lizotte, T. Sakuma, and B. Mori. 1985. Chlorinated dibenzo-p-dioxins, chlorinated dibenzo-furans, and pentachlorophenol in Canadian chicken and pork samples. Jour. Agric. Food Chem. 33 1021-1026. 

Mhin BJ, Lee JE, Choi W. Understanding the congener-specific toxicity in polychlorinated dibenzo-p-dioxins Chlorination pattern and molecular quadrupole moment. J Am Chem Soc 2002 124 144-8. 

Dichlorodibenzo-p-dioxin was prepared from isotopic potassium 2,4-dichlorophenate uniformly labeled with Ullman conditions gave a 20.5% yield. Small amounts of dichlorophenoxy chlorophenol were removed from the product by extraction with sodium hydroxide before purification by fractional sublimation and recrystallization from anisole. Chlorination of 2,7-dichlorodibenzo-p-dioxin in chloroform solution containing trace amounts of FeCls and 12 yielded a mixture of tri-, tetra-, and pentachloro substitution products. Purification by digestion in boiling chloroform, fractional sublimation, and recrystallization from anisole was effective in refining this product to 92% 2,3,7,8-tetrachloro isomer, which also contained 7% of the tri- and 1% of the penta-substituted dibenzo-p-dioxin. Mass spectroscopy was used exclusively to monitor the quality of the products during the synthesis. 

Designation, Chromatographic Separation, and Analysis. The abbreviation DBpD is used for dibenzo-p-dioxin, and the positions of chlorine... 

Figure 5. Carbon-chlorine bond lengths (A) of chlorinated dibenzo-p-dioxins as a function of the number of chlorine substituents.

Studies were made on a series of chlorinated dibenzo-p-dioxin cation radicals in trifluoromethanesulfonic acid (TFMS acid). TFMS acid was... 

The visible absorption maxima for a series of chlorinated dibenzo-p-dioxins in TFMS acid are tabulated in Table I. The visible absorption spectra of these compounds vary with the position and number of chlorine atoms. In general, a bathochromic shift was observed as more chlorine atoms were attached to the dibenzo-p-dioxin nucleus. 

Chlorinated dibenzo ip-dioxins are contaminants of phenol-based pesticides and may enter the environment where they are subject to the action of sunlight. Rate measurements showed that 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is more rapidly photolyzed in methanol than octachlorodi-benzo-p-dioxin. Initially TCDD yields 2,3,7-trichlorodiben-zo-p-dioxin, and subsequent reductive dechlorination is accompanied by ring fission. Pure dibenzo-p-dioxin gave polymeric material and some 2,2 -dihydroxybiphenyl on irradiation. Riboflavin-sensitized photolysis of the potential precursors of dioxins, 2,4-dichlorophenol and 2,4,5-trichloro-phenol, in water gave no detectable dioxins. The products identified were chlorinated phenoxyphenols and dihydroxy-biphenyls. In contrast, aqueous alkaline solutions of purified pentachlorophenol gave traces of octachlorodibenzo-p-dioxin on irradiation. 

Variations in the manufacturing process of 2,4,5-trichloro- and pentachlorophenol (but not 2,4-dichlorophenol) have sometimes resulted in contamination of the product by small amounts of heterocyclic impurities (4,5). Of these, the chlorinated dibenzo-p-dioxins such as TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin) have received much scientific and public attention because of their real or potential toxicity 6, 7), [Chick edema factor, a curious toxicological problem to poultry producers for several years, has been shown to be composed of chlorodibenzo-p-dioxins (8).]... 

Figure 1. Photolysis rates of chlorinated dibenzo-p-dioxins in methanol under ultraviolet light 2J-dichlorodibenzo-p-dioxin (III) (5 mg/liter), 2,3,7,8-tetrachlorodiben-zo-p-dioxin (I) (5 mg/liter), 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (IV) (2.2 mg/ liter) (20), 1971 by AAAS...

Industrial workers involved in chlorinated aromatic production including chlorophenol suffered dioxin-induced chloracne 2,3). Chloracne and other serious health disturbances have been attributed to polychloro-dibenzo-p-dioxins in workers involved in manufacturing 2,4,5-T 4, 5). Dioxins are toxic to chick embryos, guinea pigs, rabbits, and monkeys 6, 7, 8, 9, 10). 

This paper discusses the effects of the pyrolysis of wood and paper treated with pentachlorophenol or sodium pentachlorophenate along with the exposure of sodium pentachlorophenate to ultraviolet light. The effect of heat, light, and air with respect to some of the chlorinated dibenzo-p-dioxins will be considered. 

Light Stability of Chlorinated Dibenzo-l -dioxins. A known concentration of chlorinated dibenzo-p-dioxin was placed in a quartz 1-cm path length cell. A General Electric R.S. sunlamp was placed either 0.5 or 1.0 meters from the face of the cell. The stability of the chlorinated dibenzo-p-dioxin was monitored using ultraviolet spectroscopy. 

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. 

In addition to its extremely high oral toxicity, skin contact with substances containing 2,3,7,8-tetrachlorodibenzo-p-dioxin may allow toxicity in the form of chloracne, a condition characterized by eruptions of the skin on the face, neck, and back. Also, chlorinated dibenzo-p-dioxins have been associated with the chick edema factor, a disease of chicks associated with contaminated fats or oils used in the manufacture of their feed. 

Higher chlorinated dibenzo-p-dioxins, such as the octachloro derivative, can be formed in manufacturing pentachlorophenol from hexachloro-... 

This volume should do much to advance the knowledge of these types of molecules, and additional research should be stimulated to explain further the chemical, physical, and biological properties of the chlorinated dibenzo-p-dioxins. 

The bleaching process, in contrast, poses major difficulties. Traditional paper bleaching uses chlorine gas, which is reduced to chloride anions, cr, as it oxidizes the colored pigments in wood pulp. The chloride anion is not a pollutant, as it is a major species in the oceans. Unfortunately, chlorine processing also generates small quantities of chlorine-containing dioxins such as 2,3,7,8-tetrachloro-dibenzo-p-dioxin, whose stmcture (below) appears less formidable than its name ... 

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