Trichloropropene

As shown, ia the case of chlotination of aEyl chloride, the resonance states of the chloroaEyl radical iatermediates are not symmetrical and their propagation reactions lead to the two different dichloropropene isomers ia an approximate 10 90 ratio (26). In addition, similar reactions result ia further substitution and addition with products such as trichloropropanes, trichloropropenes, tetrachloropropanes, etc ia diminisbing amounts. Propylene dimerization products such as 1,5-hexadiene, benzene, 1-chloropropane, 2-chloropropane, high boiling tars, and coke are also produced ia smaE amounts. 

In the rabbit, the nonplanar PCB 2,2, 5,5 -tetrachlorobiphenyl (2,2, 5,5 -TCB) is converted into the 3, 4 -epoxide by monooxygenase attack on the meta-para position, and rearrangement yields two monohydroxymetabolites with substitution in the meta and para positions (Sundstrom et al. 1976). The epoxide is also transformed into a dihydrodiol by epoxide hydrolase attack (see Chapter 2, Section 2.3.2.4). This latter conversion is inhibited by 3,3,3-trichloropropene-l,2-oxide (TCPO), thus providing strong confirmatory evidence for the formation of an unstable epoxide in the primary oxidative attack (Forgue et al. 1980). 

We recently demonstrated that photocatalyzed destruction rates of low quantum efficiency contaminant compoimds in air can be promoted substantially by addition of a high quantum efficiency contaminant, trichloroethylene (TCE), in a single pass fixed bed illuminated catalyst, using a residence time of several milliseconds [1-3]. Perchloroethylene (PCE) and trichloropropene (TCP) were also shown to promote contaminant conversion [2]. These results establish a novel potential process approach to cost-effective photocatalytic air treatment for contaminant removal. 

Trichloropropene yields dibromides (72) and (73), with the latter resulting from partial isomerization of the intermediate free radical<110) ... 

In a study in which liver microsomes, prepared from male Wistar rats (200-250 g), were incubated with 5 x 10 mol/L2,3-dibromopH]propan-l-olandanNADPH-gene-rating system, covalent binding to protein was determined. Addition of the epoxide hydrolase inhibitor l,l,l-trichloropropene-2,3-epoxide led to an increase in the proteinbinding rate of 2,3-dibromopropan-l-ol (Soderlund etal., 1981). 

It has been proposed that metabolic activation of diphenylhydantoin may be responsible for the teratogenicity. After the administration of radioactively labeled diphenylhydantoin to pregnant mice, radioactive drug or a metabolite was found to be covalently bound to protein in the embryo. It was shown that both the teratogenicity and embryolethality of diphenylhydantoin could be increased by using an inhibitor of epoxide hydrolase (see chap. 4), trichloropropene oxide. Similarly, the covalent binding of radiolabeled diphenylhydantoin to protein was also increased by this treatment. 

Neudecker, T. Henschler, D. (1986) Mutagenicity of chloroolefms in the Salmonellalvaaawaa.-lian microsome test. III. Metabolic activation of the allylic chloropropenes allyl chloride, 1,3-dichloropropene, 2,3-dichloro-l-propene, 1,2,3-trichloropropene, l,l,2,3-tetrachloro-2-pro-pene and hexachloropropene by S9 mix via two different metabolic pathways. Mutat. Res., 170, 1-9... 

The condensation of 2,3,3-trichloropropenal with cyclic active methylene compounds affords fused pyran-2-ones (58CB320, 58CB330, 60CB2294). Instead of elimination of water, loss of hydrogen chloride is observed in accord with the previously postulated mechanism. 

Trichloropropene reacts similarly to HFR While internal F-olefins are not active enough for reaction with B(0S02CF3)3, more active 2,3-dichloro-F-butene-2 interacts with this Lewis acid at ambient temperature to give monotriflate 98 in a reasonable yield ... 

A number of inhibitors of this enzyme are known. They include epoxides that are hydrolyzed by the enzymes, such as trichloropropene oxide, metal ions such as Hg2+, Zn2+, and Cd2+ and 2-bromo-4 -acetophenone, a potent inhibitor that binds to imidazole nitrogen atoms. Microsomal epoxide hydrolase can be induced by compounds such asphenobarbital, Arochlor 1254,2(3)-t-butyl-4-hydroxyanisole (BHA), and 3,5-di-f-butyl-hydroxytoluene (BHT). Many microsomal epoxide hydrolase inducers are inducers also of CYP and produce a general proliferation of the endoplasmic reticulum. Induction does, however, involve an increase in the mRNA specific for the hydrolase. 

The coexistence of various pollutants does not have to be deleterious, but, in certain cases, can be quite beneficial. The first evidence for this claim came probably from the work of Lichtin et al. (1994) who found that the edition of 0.03% by volume to an air-stream containing 0.1% iso-octane caused an enhancement in the photocatalytic oxidation of the latter. Likewise, a significant rate enhancement was recorded in the photocatalytic degradation of chloroform and dichloromethane in the presence of TCE. Similar effects were recorded also with other chlorinated olefins, such as perchloroethylene (PCE) and trichloropropene (TCP), which enhanced the photooxidation of toluene in a manner similar to that of TCE (Sauer et al., 1995). 

The radical addition of HBr to 3,3,3-trichloropropene, involves migration of a chlorine atom in an intermediate step. 

The synthesis of diallate and triallate differs from the general thiocarbamate synthesis routes described. Diallate is prepared from di-isopropylaminc, carbonyl sulfide and 1,2,3-trichloropropene, and triallate from di-isopropylamine, carbonyl sulfide and 1,1,2,3-tetrachloroprop-l-ene in the presence of a base. 

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