Chlorinated terpenes

On chlorinating camphene (35) to a chlorine content of 67-69%, a yellowish, waxy product is obtained it has a slight odour of terpene and melts at 65-90°C. The product of the elementary composition C,oH,(,Clg (36) became known as an insecticide under the name toxaphene. 

According to Parker and Beacher (1947), toxaphene is a mixture of the isomers of octachlorocamphene. Investigations by Casida et al. (1974) revealed that the product is a mixture of at least 175 polychlorobornanes, each containing 6,7,8 or 9 chlorine atoms. Using C1 and C labelled toxaphene, it has been proved that about half of the carbon-chlorine bonds are metabolically labile and that most of the components contain biodegradable sites. 

The volatility of toxaphene is low, its vapour tension being 1.33 10 Pa. Under the influence of alkalies, continuous light, or temperatures above 155°C, it loses one molecule of hydrochloric acid and forms a product devoid of insecticidal activity. 

In the insect organism toxaphene is translocated primarily by the haemolymphs. It affects cardiac function and oxygen consumption and acts as a stomach and contact poison its effect is of long duration. 

From the ecological point of view, an important property of toxaphene is that of the insecticides used at present, it is the least toxic to bees. Additionally, its terpene-like odour is repellent to bees, so that it is recognised as a substance which does them little harm and can thus be used on plants in bloom. 

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Chlorinated Terpenes. A group of incompletely characterized insecticidal compounds has been produced by the chlorination of the naturally occurring terpenes. Toxaphene [8001-35-2] is prepared by the chlorination of the bicycHc terpene, camphene [79-92-5] to contain 67—69% chlorine and has the empirical formula C QH QClg. The technical product is a yellowish, semicrystalline gum (mp 65—90°C, d 1.64) and is a mixture of 175 polychloro... 

Toxaphene has been in use since 1949. It is a complex mixture that consists of at least 670 chlorinated terpenes (Jansson Wideqvist, 1983). It was used as a nonsystemic stomach and contact insecticide. As it is nontoxic to plants (except to cucurbius), it was used to control many insects that inhabited cotton, corn, fruit, vegetables and small grains, and to control the Cussia obtusifola soybean pest. Toxaphene solutions were usually mixed with other pesticides because it can help to solubilise other insecticides with lower water solubility (e.g. DDT, lindane, etc.) (ATSDR, 1996b). 

Strobane . Terpene polychlorinates Dichloricide Aerosol Dichloricide Mothproofer Insecticide 3960-X14. A mixture of chlorinated terpene isomers. Preparation by chlorinating a mixture of cam phene and pinenes contg di-pentene Schultz, Bloor, U.S. pat. 2,767,115 (1956 to B. F. Goodrich). 

Pyysalo, H. and K. Antervo. 1985. GC profiles of chlorinated terpenes (toxaphene) in some Finnish environmental samples. Chemosphere 14 1723-1728. 

Another persistent chlorinated insecticide is toxaphene, a complex mixture of about 200 structurally related chlorinated terpenes (containing 6-11 chlorine atoms) derived from camphene by... 

The spectrum of chlorinated compounds reaches from simple chlorinated Ci-,C2-, Cs-alkanes to chlorinated terpenes, steroids, fatty acids, alkaloids, heterocycles, polyacetylenes, quinones, phenols to very complex structures like the vancomycin. The structures of some chlororganica are illustrated in Figure 11) [306], [307]. 

Jansson, B., R. Vaz, G. Blomkvist, S. Jensen, and M. Olsson. 1979. Chlorinated terpenes and chlordane components found in fish, guillemot, and seal from Swedish waters. Chemosphere A 2> - 90. 

Anti-wear and extreme pressure additives phosphoric esters, dithiophosphates, sulfur-containing products such as fatty esters and sulfided terpenes or chlorinated products such as chlorinated paraffins. 

Ma.nufa.cture. The preparation of sulfuryl chloride is carried out by feeding dry sulfur dioxide and chlorine into a water-cooled glass-lined steel vessel containing a catalyst, eg, activated charcoal. Alternatively, chlorine is passed into Hquefted sulfur dioxide at ca 0°C in the presence of a dissolved catalyst, eg, camphor, a terpene hydrocarbon, an ether, or an ester. The sulfuryl chloride is purified by distillation the commercial product is typically 99 wt % pure, as measured by ASTM distillation method D850. 

Reduction of carbonyl groups Terpene and aromatic aldehydes (lOOppm) were reduced by microalgae. In a series of chlorinated benzaldehyde, m - or p-chlorobenzaldehyde reacted faster than the o-derivative. Due to toxicity, the substrate concentrations are difficult to increase. Asymmetric reductions of ketones by microalgae were reported. Thus, aliphatic " and aromatic " ketones were reduced. 

Various attempts have been made to improve the stability of amorphous sulphur. Addition of small amounts of halogens, i.e., chlorine, bromine, iodine, treatment with sulphur monochloride or the addition of a terpene have some effect on the rate of conversion. As far as is known, none of the modified materials are commercially available. 

Yellow, waxy, nonflammable solid with a chlorine or terpene-like odor. Odor threshold concentration from water is 140 pg/L (quoted, Keith and Walters, 1992). 

Kostiainen (1995) identified more than 200 individual VOCs indoors in 26 houses. In addition, they compared the VOC concentrations in normal houses to those where complaints of odors or illness had been registered. A number of different VOCs were present at increased concentrations in the houses with complaints compared to the normal houses these included a variety of aromatic hydrocarbons, methylcyclohexane, n-propylcyclohexane, terpenes, and chlorinated compounds such as 1,1,1-trichloroethane and tetra-chlorethene. 

Bergamot oil is adulterated in various ways, e.g., with oil of turpentine, oil or terpenes of lemon, orange terpenes, fatty oils, waxes, resin, gurjun and Canada balsam, cedarwood oil, mineral oils, chlorinated compounds of oil of turpentine, organic acids, various esters (diethyl succinate, triethyl citrate, diethyl oxalate, terpinyl acetate, esters of oleic, phthalic, tartaric and acetic acids). Such adulteration is usually made judiciously, the genuine oil being treated with such quantities of one or more picked adulterants as will not alter too markedly the characters of the oil itself.1... 

Toxaphene (CioHio(- 18) is a mixture of polychlorinated camphenes (bicyclic terpenes). Currently in restricted use as an insecticide, it is toxic to fish, birds and wildlife and may be fatal to shrimp, and crab, etc. (ref. 103, p. 26). Its toxicity and routes of entry in mammals are typical of the cyclic chlorinated hydrocarbons as a class ... 

Another contamination of citrus peel oils comes from chlorine-treated water used in the oil recovery process and sanitizers used in postharvest handling and process equipment cleaning, which serve as a potential source of hypochlorous acid (HOCl) (73). HOCl can react with a variety of terpenes similar to d-limonene in structure, including hmonene, a-pinene, and a-terpineol, resulting in the formation of terpene chlorohydrins. The contamination of terpene chlorohydrins could be reduced through reduction of the chlorine levels in the treatment water (74). 

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