Methylation, pentachlorophenol

Cserjesi AJ, EL Johnson (1972) Methylation of pentachlorophenol by Trichoderma virginatum. Can J Microbiol 18 45-49. 

Suzuki T (1978) Enzymatic methylation of pentachlorophenol and its related compounds by cell-free extracts of Mycobacterium sp isolated from soil. J Pesticide Sci 3 441-443. 

Suzuki T (1983) Methylation and hydroxylation of pentachlorophenol hy Mycobacterium sp. isolated from soil. J Pesticide Sci 8 419-428. 

Pentachlorophenol was also subject to methylation by a culture medium containing Trichoderma wr/c/e affording pentachloroanisole (Cserjesi and Johnson, 1972). 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

CP 1309, see Pentachlorophenol CPD-244, see 2-Nittopropane CPD-926, see Dibenzofuran 4-CPPE, see 4-Chlorophenyl phenyl ether p-CPPE, see 4-Chlorophenyl phenyl ether Crag sevin, see Carbaryl Crawhaspol, see Trichloroethylene 2-Cresol, see 2-Methylphenol 4-Cresol, see 4-Methylphenol oCresol, see 2-Methylphenol p-Cresol, see 4-Methylphenol Crestoxo, see Toxaphene Crestoxo 90, see Toxaphene oCresylic acid, see 2-Methylphenol p-Cresylic acid, see 4-Methylphenol oCresyl phosphate, see Tri-ocresyl phosphate Crisalin, see Trifluralin Crisalina, see Trifluralin Crisfuran, see Carbofuran Crisulfan, see a-Endosulfan, p-Endosulfan Crisuron, see Diuron Crolean, see Acrolein Crop rider, see 2,4-D Crotenaldehyde, see Crotonaldehyde Crotilin, see 2,4-D Crotonal, see Crotonaldehyde Crotonic aldehyde, see Crotonaldehyde CRS, see Phenol Crunch, see Carbaryl Cryptogil OL, see Pentachlorophenol CS, see oChlorobenzylidenemalononitrile, Methyl mercaptan... 

Preventol CMK, see p-Chloro-/n-cresol Preventol I, see 2,4,5-Trichlorophenol Priltox, see Pentachlorophenol Primary amyl acetate, see Amyl acetate Primary isoamyl alcohol, see Isoamyl alcohol Primary isobutyl alcohol, see Isoamyl alcohol Prioderm, see Malathion Prist, see Methyl cellosolve Profume A, see Chloropicrin Profume R 40B1, see Methyl bromide Prokarbol, see 4,6-Dinitro-o-cresol... 

Acetamido-4-amino-6-chloro-s-triazine, see Atrazine Acetanilide, see Aniline, Chlorobenzene, Vinclozolin Acetic acid, see Acenaphthene, Acetaldehyde, Acetic anhydride. Acetone, Acetonitrile, Acrolein, Acrylonitrile, Aldicarb. Amyl acetate, sec-Amyl acetate, Bis(2-ethylhexyl) phthalate. Butyl acetate, sec-Butyl acetate, ferf-Butyl acetate, 2-Chlorophenol, Diazinon. 2,4-Dimethylphenol, 2,4-Dinitrophenol, 2,4-Dinitrotoluene, 1,4-Dioxane, 1,2-Diphenylhydrazine, Esfenvalerate. Ethyl acetate, Flucvthrinate. Formic acid, sec-Hexyl acetate. Isopropyl acetate, Isoamyl acetate. Isobutyl acetate, Methanol. Methyl acetate. 2-Methvl-2-butene. Methyl ferf-butvl ether. Methyl cellosolve acetate. 2-Methvlphenol. Methomvl. 4-Nitrophenol, Pentachlorophenol, Phenol. Propyl acetate. 1,1,1-Trichloroethane, Vinyl acetate. Vinyl chloride Acetoacetic acid, see Mevinphos Acetone, see Acrolein. Acrylonitrile. Atrazine. Butane. 

Dichloromaleic acid, see Pentachlorophenol Dichloromethoxyphenol, see Bifenox Dichloromethylamine, see Methomvl Dichloro-l-methyl-2-benzimidazolinone, see... 

Carbon tetrachloride. Chloroform, 2-Chlorophenol, Cyclohexanol, Cyclopentene, 1,1-Dichloroethylene, irans-l, 2-Dichloroethylene, IV.yV-Dimethylaniline, lV,lV-Dimethylformamide, 2,4-Dimethylphenol, 2,4-Dinitrotoluene, 1,4-Dioxane, 1,2-Diphenylhydrazine, Ethyl formate. Formaldehyde, Glycine, Methanol, Methylene chloride. Methyl formate, 2-Methvlphenol. Monuron, 4-Nitrophenol, Oxalic acid, Parathion, Pentachlorophenol, Phenol, l idine. Styrene, Trichloroethylene, Vinyl chloride Formylacetic acid, see cis-l,3-Dichloropropylene, irans-1,3-Dichloropropylene IV-Formylcarbamate of 1-naphthol, see Carbaryl Formyl chloride, see Chloroethane, Chloroform, sym-Dichloromethyl ether, ds-1,3-Dichloropropylene, irans-ES-Dichloropropylene, Methyl chloride. Methylene chloride. Trichloroethylene, Vinyl chloride lV-Formyl-4-chloro-o-toluidine, see Chlornhenamidine. 

Dichloropropylene, frans-1,3-Dichloropropylene, Dieldrin, Diuron, Epichlorohydrin, Formaldehyde, Hexachlorocyclopentadiene, Eindane, Methoxychlor, Methyl chloride. Methylene chloride, Pentachlorophenol, 2,4,5-T, 1,1,2,2-Tetrachloroethane, Toxaphene, 1,1,1-Trichloroethane, 1,1,2-Trichloroethane, 1,2,3-Trichloropropane, Trichloroethylene, 1.1.1-Trichloro-2.2.2-trifluoroethane. Trichlorofluoromethane, Vinyl chloride Hydrofluoric acid, see Trichlorofluoromethane, 1.1.1-Trichloro-2.2.2-trifluoroethane. Trifluralin Hydrogen, see Benzene, Chloroform, Difenzoquat methyl sulfate. 1,4-Dioxane, Ethylamine, Ethylbenzene, Ethylenimine, Formaldehyde. Formic acid, Hexachlorobenzene, Methyl bromide. Pentachlorobenzene. TCDD. Tetrachloroethylene. 

According to the vendor, the CAV-OX technology treats contaminants such as halogenated solvents, phenol, pentachlorophenol (PCP) pesticides trichloroethene (TCE) polychlorinated biphenyls (PCBs) explosives benzene, toluene, ethylbenzene, and xylene (BTEiX) methyl tertiary butyl ether bacteria and virus strains and cyanide. 

Figure 8.9 The pH dependence of the /z-octanol-water distribution ratio of pentachlorophenol (PCP, pKj = 4.75), 4-chloro-a-(4-chlo-rophenyl) benzene acetic acid (DDA, pKb = 3.66), 2-methyl-4,6-dinitrophenol (DNOC, pKia = 4.46), and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T, pKia = 2.83). (from Jafvert et al., 1990).

Di-ter2-butylphenol 2,4,5-Trichlorophenol Phenyl salicylate Methyl 4-hydroxybenzoate 4-Hydroxyacetophenone Ethyl 4-hydroxybenzoate 4-Hydroxybenzaldehyde Pentachlorophenol 4-Chloro-2-nitrophenol 4-Nitrophenol... 

SFE/derivatization of several chlorinated acid pesticides (those listed in EPA method 515.1) have been performed using conditions similar to those used for the bacterial phospholipids. The derivatized products from the SFE procedure for several representative organics are shown in Figure 6. As would be expected using the TMPA/methanol reagent, the carboxylic acids form the methyl esters (2,4-D and dicamba) while the phenols form the methyl ethers (pentachlorophenol). Esters of the carboxylic acids (e.g., the di-isopropyl amine ester of 2,4-D) also form the methyl esters. For ethers, two derivatized products resulted since the ether linkage could be cleaved on either side of the oxygen and methylated as shown by acifluorfen. 

Methods of Extraction and Analyses. Chloropyrifos, Ronnel, chlorpropham and 2,4,5-T were extracted from the cloth or the cellulose pad with hexane. Pentachlorophenol residues were extracted with benzene. Pentachlorophenol was methylated with diazomethane prior to determination by gas chromatography while the other compounds were determined dirgctly. Dinoseb, on the other hand was extracted with chloroform and partitioned into 2% Na2 Co3 solution. The yellow extract was analyzed colorimetri-cally using the method of Potter (14). 

FIGURE 13.14 A typical LC-MS chromatogram obtained in the scan mode of a preconcentrated aqueous standard solution (a) and of a preconcentrated spiked river water sample (b), as well as of an unspiked preconcentrated river water sample (c). Peak labels denote Ph, Phenol 2,4-DMP, 2,4-dimethylphenol 2-CP, 2-chlo-rophenol 4-CR,4-chlorophenol 4-NP,4-nitrophenol 2-NP,2-nitrophenol 4-C-3-MP,4-chloro-3-methylphenol 2,4-DCP, 2,4-dichlorophenol 2,4-DNP, 2,4-dinitrophenol 2,4,6-TCP, 2,4,6-trichlorophenol 2-M-4.6-DNP, 2-methyl-4,6-dinitrophenol and PCP, pentachlorophenol. Spike level 1 pg/L 10 mL preconcentrated. 

For example, the ratio of the n-octanol/watcr distribution coefficient of the nondissociated species to that of the ionic species is nearly 10,000 for 3-methyl-2-nitrophenol, but only about 1000 for pentachlorophenol because of the greater significance of the hydrophobicity of the ionized form of pentachlorophenol. The logarithm of the -octanol/water distribution coefficient of pentachlorophenol as the phenolate is about 2 (determined at pH 12, and 0.1 M KC1), which indicates significant distribution of the ionized form into the n-octanol phase [8,37], Extraction of such highly hydrophobic ionogenic organic compounds can result from mixed-mode mechanisms that incorporate both the hydrophobic and ionic character of the compound. 

The best method for determining pentachlorophenol is conversion into the methyl ether followed by analysis using gas chromatography with an electron-capture detector, or gas chromatography coupled with mass spectrometry [2], Both of these methods require an extensive amount of pretreatment and highly-trained personnel f or the operation of the equipment. 

Phenol adonifen, butralin, cyfluthrin, 2.4 D, diafenthiuron, dichlorprop, diclofop-methyl, dinocap, famphur, fenothiocarb, fenoxycarb, fenpyroximate, nicosulfuron, nitrofen, pentachlorophenol, 2 phenyl phenol, silafluofen, sulcofuron... 

Figure 10. Proton-nmr spectra recorded (A) before and (D) during tne photolysis of 4-phenylacetophenone and pentachlorophenol in isopropanol. The methyl protons spectrum at 6 2.0 was recorded at a much lower sensitivity than that of the aromatic protons at...

Alachlor, benzene hexachloride, cycloodines, aldrin, chlordane, dieldrin, endrin, endosulfan, heptachlor, isodrin, telodrin and toxaphene, DDT and metabolites, dicofol, dimethoate, lindane, methoxychlor, mirex, pentachlorophenol, perthane Azinphosmethyl, bromophos ethyl, chlorpyrifos, crotoxyphos, demeton, diazinon, dichlorvos, ethion, fenitrothion, fensulfothin, fenthion, flusulfothin, methamidophos, mevinphos monocrotophos and dichrotophos, oxamyl, phorate, parathion (ethyl), parathion (methyl), phosphomidon, quinolphos temephos Aldicarb, benomyl, carbaryl, chlorpropham, fenvalerate, methomyl... 

Fig. 32.5 Influence of GC column internal diameter on separation 1. phenol 2. 2-chlorophenol 3. 2-nitrophenol 4. 2,4-dimethylphenol 5. 2,4-dichlorophenol 6. 4-chloro-3-methylphenol 7. 2,4,6-trichlorophenol 8. 2,4-dinitrophenol 9. 4-nitrophenol 10. 2-methyl-4,6-dinitrophenol 11. pentachlorophenol.

Protonation becomes a rapid reaction in protic solvents and in the presence of acids, as demonstrated for, e.g., -butyl acrylate in aqueous solution [207], methyl acrylate in EtOH [208], cinnamates in the presence of phenol in DMF [209], and benzaldehyde in ethanolic buffer solution [210]. Rate constants for protonation of aromatic radical anions (anthracene [211], naphthalene, 2-methoxynaphthalene, 2,3-dimethoxynaphthalene) by a number of proton donors including phenols, acetic acid, and benzoic acids in aprotic DMF were found to vary from 5.0 X 10 M- s-> (for anthracene, in the presence of p-chlorophenol) to 6.2 x lO s (for anthracene, in the presence of pentachlorophenol) [212]. For dimedone, PhOH, or PhC02H the rate of protonation depends on the hydrogen-bond basicity of the solvent and increases in the order DMSO < DMF MeCN [213],... 

The long-term effectiveness of TBTMA as a biocide has been confirmed (23). The deterioration of southern pine wood specimens impregnated with TBTMA has been compared with specimens that were treated with pentachlorophenol methacrylate (PGPMA) or pen-tabromophenol methacrylate (PGBMA). The three esters were incorporated as the copolymer by in situ copolymerization with methyl methacrylate (MMA) at different molar ratios of the comonomers. 

Detoxification involves a chemical change to a molecule. In equation 3, pentachlorophenol (PCP), a powerful biocide used in wood preservative, undergoes O-methylation. This transforms PCP to a far less toxic compound pentachloroanisole. Detoxification by one group of microorganisms often allows other organisms to continue biodegradation. 

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