- Influence of n-Butyl and n-Hezil Alcohols in the Dehydrohalogenation of DDT in Cationic Micelles of N-Cetyl-N,N,N-trimethylammonium Bromide, Chloride, and Hydroxide
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The incorporation of n-butyl and n-hexyl alcohols on cationic micelles of hexadecyltrimethylammonium bromide, chloride, and hydroxide (CTAB, CTAC, and CTAOH) decreases the rate of the basic dehydrohalogenation of DDT in simple cationic micelles.From the kinetic results and on the basis of the Berezin model the mean nolar volume of micellar pseudophase for simple micelles and surfactant/alcohol system has been evaluated.
- Otero, C.,Rodenas, E.
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Read Online
- Aerobic Electrochemical Transformations of DDT to Oxygen-Incorporated Products Catalyzed by a B12 Derivative
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Electrochemical transformations of DDT into oxygen-incorporated products, amides and esters, catalyzed by a B12 derivative, heptamethyl cobyrinate perchlorate, have been developed under aerobic conditions. The dechlorinative oxygenation of DDT forms the acyl chloride as an intermediate for the synthesis of the amide and ester in the reaction with the amine and alcohol, respectively. This electrochemical method demonstrated with 20 oxygen-incorporated dechlorinated products up to 88% yields with 15 new compounds and was also successfully applied to the conversion of methoxychlor to an amide and ester.
- Hisaeda, Yoshio,Moniruzzaman, Mohammad,Ono, Toshikazu,Shimakoshi, Hisashi,Yano, Yoshio
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supporting information
p. 2784 - 2791
(2022/01/19)
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- Compounds and methods for the reduction of halogenated hydrocarbons
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The present application relates to methods for the reduction of halogenated hydrocarbons using compounds of Formula (I): wherein the reduction of the halogenated compounds is carried out, for example, under ambient conditions without the need for a transition metal containing co-factor. The present application also relates to methods of recovering precious metals using compounds of Formula (I) that are absorbed onto a support material.
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Page/Page column 20-21
(2017/12/27)
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- Kinetic and quantum chemical studies of the mechanism of dehydrochlorination of 2,2-diaryl-1,1,1-trichloroethanes with nitrite ions
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The E2 mechanism has been proposed for the dehydrochlorination of 2,2-diaryl-1,1,1-trichloroethanes with nitrite ion, leading to 2,2-diaryl-1,1-dichloroethenes, on the basis of experimental kinetic study and quantum chemical simulation.
- Kazin,Kuzhin,Sirik,Guzov
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p. 1277 - 1281
(2016/10/26)
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- Electrochemical dechlorination of 4,4′-(2,2,2-trichloroethane-1,1-diyl)bis(chlorobenzene) (DDT) at silver cathodes
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Cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the reduction of 4,4′-(2,2,2-trichloroethane-1,1-diyl)bis(chlorobenzene) (DDT) at silver cathodes in dimethylformamide (DMF) containing 0.050 M tetramethylammonium tetrafluoroborate (TMABF4). In addition, this work has been extended to the individual reductions of two degradation products, namely 4,4′-(2,2-dichloroethane-1,1-diyl)bis(chlorobenzene) (DDD) and 4,4′-(ethene-1,1-diyl)bis(chlorobenzene) (DDNU). At a scan rate of 100 mV s-1, cyclic voltammograms for irreversible reduction of DDT at a silver electrode exhibit four prominent cathodic peaks in DMF and CH3CN, and three prominent cathodic peaks in DMSO. On the other hand, reduction of DDD and DDNU at silver in DMF-0.050 M TMABF4displays four and two irreversible peaks, respectively. Carbon-chlorine bonds of the -CCl3moiety of DDT and of the -CHCl2moiety of DDD are reduced more easily at silver than at glassy carbon. Bulk electrolyses of DDT at a silver gauze cathode in DMF-0.050 M TMABF4afford a potential-dependent mixture of products that includes DDD, DDNU, 4,4′-(2,2-dichloroethene-1,1-diyl)bis(chlorobenzene) (DDE), 4,4′-(2-chloroethene-1,1-diyl)bis(chlorobenzene) (DDMU), 4,4′-(2-chloroethane-1,1-diyl)bis(chlorobenzene) (DDMS), 1-chloro-4-(1-phenylvinyl)benzene (PVB), 1,1′-diphenylethylene (DPE), and 1,1′-ethylidenebisbenzene (EBB). However, at more negative potentials, the principal products are completely dechlorinated DPE and EBB. Dechlorination of DDT at silver appears to proceed via a series of steps involving carbanion intermediates arising from direct reduction of alkyl and aryl carbon-chlorine bonds along with hydroxide-promoted E2 elimination of chloride. When DMF-d7was used as solvent, no evidence for deuterium atom incorporation into any product was seen, which indicates that radical intermediates do not play a significant role in the reduction of DDT.
- McGuire, Caitlyn M.,Peters, Dennis G.
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p. 423 - 430
(2014/12/10)
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- Design of a bimetallic Au/Ag system for dechlorination of organochlorides: Experimental and theoretical evidence for the role of the cluster effect
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The experimental study of dechlorination activity of a Au/Ag bimetallic system has shown formation of a variety of chlorinated bimetallic Au/Ag clusters with well-defined Au:Ag ratios from 1:1 to 4:1. It is the formation of the Au/Ag cluster species that mediated C-Cl bond breakage, since neither Au nor Ag species alone exhibited a comparable activity. The nature of the products and the mechanism of dechlorination were investigated by ESI-MS, GC-MS, NMR, and quantum chemical calculations at the M06/6-311G(d)&SDD level of theory. It was revealed that formation of bimetallic clusters facilitated dechlorination activity due to the thermodynamic factor: C-Cl bond breakage by metal clusters was thermodynamically favored and resulted in the formation of chlorinated bimetallic species. An appropriate Au:Ag ratio for an efficient hydrodechlorination process was determined in a joint experimental and theoretical study carried out in the present work. This mechanistic finding was followed by synthesis of molecular bimetallic clusters, which were successfully involved in the hydrodechlorination of CCl4 as a low molecular weight environment pollutant and in the dechlorination of dichlorodiphenyltrichloroethane (DDT) as an eco-toxic insecticide. High activity of the designed bimetallic system made it possible to carry out a dechlorination process under mild conditions at room temperature.
- Romashov, Leonid V.,Khemchyan, Levon L.,Gordeev, Evgeniy G.,Koshevoy, Igor O.,Tunik, Sergey P.,Ananikov, Valentine P.
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p. 6003 - 6012
(2015/02/19)
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- Synthesis, electrochemistry, spectroelectrochemistry and catalytic properties in DDT reductive dechlorinationin of iron(II) phthalocyanine, 2,3-and 3,4-tetrapyridinoporphyrazine complexes
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Iron(II) 2,3-and 3,4-tetrapyridinoporphyrazine complexes (2,3-PyD and 3,4-PyD) were synthesized and characterized as to their electrochemistry, UV-visible spectroelectrochemistry and catalytic properties towards the reductive dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (p,p′-DDT) in pyridine, dimethyl sulfoxide (DMSO), N,N′- dimethylacetamide (DMA) and N,N′-dimethylformamide (DMF). These properties were compared with those of the unsubstituted iron(II) phthalocyanine ((Pc)Fe). Electrochemistry indicates that there are up to three reductions and one oxidation in the three investigated derivatives. The easiest reduction takes place for 3,4-PyD while the most difficult one occurs for (Pc)Fe in all of the solvents investigated. The first reduction is metal-centered corresponding to the formation of [P(-2)Fe(I)]- while the second and third reductions are ring-centered leading stepwise to the generation of [P(-3)Fe(I)] 2- · and [P(-4)Fe(I)]3-, where P = phthalocyanine or tetrapyridinoporphyrazine rings. Aggregation exists in the solutions of all three iron complexes and its extent depends upon the nature and concentration of the iron compounds and the binding property of each solvent. The order of the extent of aggregation for the three iron derivatives is 3,4-PyD > 2,3-PyD > (Pc)Fe. Stronger binding solvents such as pyridine and DMSO do not favor the aggregation. The singly and doubly reduced species of investigated complexes, [P(-2)Fe(I)]- and [P(-3)Fe(I)]2- ·, are active in DDT reductive dechlorination, the latter of which has better catalytic performance. As a result, three products, 1,1-bis(4-chlorophenyl)-2,2- dichloroethane (p,p′-DDD), 1,1-bis(4-chlorophenyl)-2,2-dichloroethylene (p,p′-DDE), and 1,1-bis(4-chlorophenyl)-2-chloroethylene (p,p′-DDMU), were obtained after the dechlorination of DDT catalyzed by each iron complex. The increasing order of catalytic performance is 3,4-PyD 2,3-PyD (Pc)Fe in pyridine, which is superior to DMSO and DMA for the DDT dechlorination reaction. An overall electrocatalytic mechanism is proposed for DDT reductive degradation based on the electrochemical and UV-visible spectroelectrochemical results.
- Shao, Jianguo,Richards, Kema,Rawlins, Dwayne,Han, Baocheng,Hansen, Christopher A.
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p. 317 - 330
(2013/07/26)
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- Reductive dechlorination of DDT electrocatalyzed by synthetic cobalt porphyrins in N,N′-dimethylformamide
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Two cobalt porphyrins, (OEP)CoII and (TPP)CoII, where OEP and TPP are the dianions of octaethylporphyrin and tetraphenylporphyrin, respectively, were examined as electrocatalysts for the reductive dechlorination of DDT (1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane) in N,N′- dimethylformamide (DMF) containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). No reaction is observed between DDT and the porphyrin in its Co(II) oxidation state but this is not the case for the reduced Co(I) forms of the porphyrins which electrocatalyze the dechlorination of DDT, giving initially DDD (1,1-bis(4-chlorophenyl)-2,2-dichloroethane), DDE (1,1-bis(4-chlorophenyl)-2, 2-dichloroethylene) and DDMU (1,1-bis(4-chlorophenyl)-2-chloroethylene) as determined by GC-MS analysis of the reaction products. A further dechlorination product, DDOH (2,2-bis(4-chlorophenyl)ethanol), is also formed on longer timescales when using (TPP)Co as the electroreduction catalyst. The effect of porphyrin structure and reaction time on the dechlorination products was examined by GC-MS, cyclic voltammetry, controlled potential electrolysis and UV-visible spectroelectrochemistry and a mechanism for the reductive dechlorination is proposed.
- Zhu, Weihua,Fang, Yuanyuan,Shen, Wei,Lu, Guifen,Zhang, Ying,Ou, Zhongping,Kadish, Karl M.
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scheme or table
p. 66 - 74
(2012/03/10)
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- Enhanced reactivity of hydrophobic vitamin B12 towards the dechlorination of DDT in ionic liquid
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The electrolytic reductive dechlorination of 1,1-bis(p-chlorophenyl)-2,2,2- trichloroethane (DDT) in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) in the presence of a cobalamin derivative afforded 1,1′-(ethylidene)bis(4-chlorobenzene) (DDO) and 1,1′-(ethenylidene)bis(4-chlorobenzene) (DDNU) with 1,1′-(2- chloroethylidene)bis(4-chlorobenzene) (DDMS); the enhanced reactivity, as well as the recyclability of the cobalamin derivative catalyst in IL, makes the present system more efficient for the development of "green" technologies. The Royal Society of Chemistry.
- Jabbar, Md. Abdul,Shimakoshi, Hisashi,Hisaeda, Yoshio
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p. 1653 - 1655
(2008/02/07)
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- Photochemical dechlorination of DDT catalyzed by a hydrophobic vitamin B12 and a photosensitizer under irradiation with visible light.
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Dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) was catalyzed by a hydrophobic vitamin B(12), heptamethyl cobyrinate perchlorate, with a visible light irradiation system containing a [Ru(ii)(bpy)(3)]Cl(2) photosensitizer, and the hydrophobic vitamin B(12) showed high catalytic efficiency and stability during the reaction.
- Shimakoshi, Hisashi,Tokunaga, Mami,Baba, Tatsushi,Hisaeda, Yoshio
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p. 1806 - 1807
(2007/10/03)
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- Hydrophobic vitamin B12· part 19: Electroorganic reaction of DDT mediated by hydrophobic vitamin B12
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The controlled-potential electrolysis of 1,1-bis(4-chlorophenyl)-2,2,2- trichloroethane (DDT) was carried out at -1.4 V vs. Ag-AgCl in the presence of a hydrophobic vitamin B12, heptamethyl cobyrinate perchlorate. DDT was dechlorinated to form 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (DDD), 1,1-bis(4-chlorophenyl)-2,2-dichloroethylene (DDE), 1-chloro-2,2-bis(4- chlorophenyl)ethylene (DDMU) and 1,1,4,4-tetrakis(4-chlorophenyl)-2,3-dichloro- 2-butene (TTDB) (E/Z), and quantitative recovery of the catalyst after the electrolysis was confirmed by electronic spectroscopy. A photo-sensitive intermediate having a cobalt-carbon bond formed during the electrolysis was characterized by electronic spectroscopy. A mechanism for the formation of various dechlorinated products was investigated by using deuterium solvents and various spectroscopic measurements such as UV-VIS and the EPR spin-trapping technique.
- Shimakoshi, Hisashi,Tokunaga, Mami,Hisaeda, Yoshio
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p. 878 - 882
(2007/10/03)
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- Kinetic method to estimate dissociation degrees of micellar aggregates in TTAB-alcohol aqueous micellar solutions
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The reactions of dehydrochlorination of 1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, DDT, and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane, DDD, with hydroxide ions were studied in various TTAB-alcohol (TTAB = tetradecyltrimethylammonium bromide) aqueous micellar solutions as a function of alcohol content. The alcohols used were heptanol, hexanol, pentanol, butanol, isobutanol, tert butanol, propanol and isopropanol. Kinetic data show that the dissociation degree of the micelles is the main factor controlling reactivity in all the TTAB-alcohol micellar solutions. This fact permits the development of a kinetic method in order to estimate the dissociation degree of the micellar aggregates present in the alcohol-TTAB aqueous micellar solutions.
- Munoz, Maria,Rodriguez, Amalia,Del Mar Graciani, Maria,Moya, Maria Luisa
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p. 204 - 209
(2007/10/03)
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- Electrochemical reduction and oxidation of DDT
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Electrolysis has been studied as a possible method to treat DDT wastes. In methanol, the major process was dehydrochlorination to DDE followed by further reduction. In an aqueous emulsion containing 1% heptane and 0.1% Triton SP-175, DDT was reduced at a deposited lead electrode with sodium sulphate as the supporting electrolyte by sequential hydrodechlorination of the aliphatic chlorine atoms. An excellent material balance was achieved, but the current efficiency was poor, even at low current densities. Electrooxidation of DDT was also investigated; in aqueous solutions or emulsion, little oxidation occurred because of competing oxidation of water at the highly positive potentials needed to oxidize DDT. In acetonitrile, electrooxidation occurred with high current efficiency by way of 'electrochemical combustion' of DDT and its intermediate oxidation products to CO2. We conclude that development of an electrolytic technology for destroying DDT wastes is unlikely.
- Merica, Simona G.,Jedral, Wojceich,Lait, Susan,Keech, Peter,Bunce, Nigel J.
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p. 1281 - 1287
(2007/10/03)
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- Ramberg-Backlund rearrangement vs. β-Elimination of haloform from trichloro and trifluoromethyl sulfones
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A new and convenient method for the preparation of trichloro and trifluoromethanesulfinates is described. These esters readily undergo rearrangement to the corresponding sulfones at room temperature, in high yields. In contrast to trichloromethyl sulfoxides which undergo base-induced β-elimination of chloroform to sulfines, the corresponding sulfones undergo an unusually facile Ramberg-Backlund rearrangement with formation of dichloromethylene products. Replacement of CCl3 by CF3 results in complete loss of reactivity, even under drastic basic conditions.
- Braverman, Samuel,Zafrani, Yossi
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p. 1901 - 1912
(2007/10/03)
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- A facile and high yielding synthesis of symmetrical and unsymmetrical diarylalkynes using diethyl dichloromethylphosphonate as precursor
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The reaction, under internal quench conditions, of diethyl dichloromethylphosphonate and symmetrical or unsymmetrical diaryl ketones in the presence of n-BuLi, leads to the corresponding symmetrical or unsymmetrical diarylalkynes via a Fritsch-Buttenherg-Wiechell rearrangement in a simple, high yielding, one-pot reaction.
- Mouriès, Virginie,Waschbüsch, Rachel,Carran, John,Savignac, Philippe
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p. 271 - 274
(2007/10/03)
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- Free radical elimination and oxidation of 1, 1, 1-trichloro-2, 2-bis(p-substituted phenyl)ethanes
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The reaction of 1, 1, 1-trichloro-2, 2-bis(p-substituted-phenyl)ethanes with bromine in carbon tetrachloride under nitrogen atmosphere and in the presence of light results in the formation of 1, 1-dichloro-2, 2-bis(p-substituted-phenyl)ethylenes. Whereas an identical reaction conducted under oxygen atmosphere, leads to the formation of benzophenone derivatives.
- Bennur, Shankar C.,Talawar, Mahadev B.,Laddi, Umesh V.,Nome, Faruk
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- Mechanochemical reaction of DDT with calcium oxide
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Evidence is presented that, in the mechanochemical destruction of DDT [2,2-bis(4-chlorophenyl)1,1,1-trichloroethane] by ball milling in the presence of calcium oxide, a complex series of reactions occurs along the pathway to a product that appears to be essentially graphitic, though aromatic chloro and hydroxy substituents are retained to some degree. The production of the various intermediates can be understood in terms of processes initiated at both CaO and steel (of the milling device) surfaces. With the exception of DOE [2,2-bis(4-chlorophenyl)1,1-dichloroethene], most of these intermediates attain maximum concentrations corresponding to 1 mol % of the original DDT and have been characterized only by their mass spectra. In the case of dichlorotolane [bis(4-chlorophenyl)ethyne], however, yields are sufficient for it to be isolated chromatographically as a pure, crystalline solid and characterized further by NMR spectroscopy. After 12 h of milling, no organic materials volatile enough to be detected by conventional GC/MS procedures are present, but the black, graphitic residue does retain some chlorine that is only slowly removed by extended milling.
- Hall, Annegret K.,Harrowfield, Jack M.,Hart, Reinhold J.,Mccormicr, Paul G.
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p. 3401 - 3407
(2007/10/03)
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- Electrolytic Dechlorination of DDT In a Bicontinuous Microemulsion
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Electrolytic reduction in a bicontinuous microemulsion of surfactant, oil, and water removed aliphatic and aromatic chlorines from DDT. Microemulsions of didodecyldimethylammonium bromide/dodecane/water used with graphite felt cathodes provided a less expensive, less toxic approach to DDT electrolysis compared to using conventional organic solvents and metal electrodes. Good rates of aliphatic dechlorination were achieved by applying -1 V vs. Ag/AgBr and using the catalyst Co(bpy)32+, but the best yield (34 percent in 3 hr) of the fully dechlorinated hydrocarbon 1,1-diphenylethane was achieved by using -2 V with oxygen in the reaction medium.
- Schweizer, Silvia,Rusling, James F.,Huang, Qingdong
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p. 961 - 970
(2007/10/03)
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- REACTION OF 1,1,1-TRICHLORO-2,2-BIS(CHLOROPHENYL)ETHANE AND ITS NITRO DERIVATIVES WITH ALKALI-METAL NITRITES
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3,3'-Dinitro-4,4'-dihydroxybenzophenone was obtained with a high yield by the reaction of 1,1,1-trichloro-2,2-bis(3-nitro-4-chlorophenyl)ethane with alkali-metal nitrites in aprotic dipolar solvents.The reaction of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane with potassium nitrite and sodium nitrite under analogous conditions leads to dehydrochlorination of the substrate, while the 1,1,1-trichloro-2,2-bis(3,5-dinitro-4-chlorophenyl)ethane is converted into 1,1-dichloro-2,2-bis(3,5-dinitro-4-hydroxyphenyl)ethylene.
- Kazin, V. N.,Sibrikov, S. G.,Kopeikin, V. V.,Mironov, G. S.
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p. 323 - 324
(2007/10/02)
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- TRANSFORMATIONS OF 1,1,1-TRICHLORO-2,2-BIS(4-CHLOROPHENYL)ETHANE, 4,4'-DICHLOROBENZOPHENONE, AND THEIR NITRO DERIVATIVES IN A SODIUM HYDROXIDE-AMIDE SOLVENT MEDIUM
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The reaction of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane with alkali in an amide solvent leads to dehydrochlorination of the substrate.In 1,1,1-trichloro-2,2-bis(3-nitro-4-chlorophenyl)ethane under the same conditions substitution of the chlorine atoms in the bridging group by dimethylamino groups, formed as a result of hydrolysis of the solvent, occurs after dehydrochlorination.In 1,1,1-trichloro-2,2-bis(3,5-dinitro-4-chlorophenyl)ethane the chlorine atoms of benzene ring are substituted by dimethylamino groups.In the presence of CuCl 4,4'-dichlorobenzophenone is converted into 4,4'-bis(dimethylamino)benzophenone. 3,3'-Dinitro-4,4'-dichlorobenzophenone reacts with the sodium hydroxide-amide solvent system with the formation of 3,3'-dinitro-4,4'-bis(dimethylamino)-benzophenone and 3,3'-dinitro-4-hydroxy-4'-dimethylaminobenzophenone, the ratio of which is determined by the reaction temperature.
- Sibrikov, S. G.,Kazin, V. N.,Kopeikin, V. V.,Mironov, G. S.,Orlova, T. N.
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p. 325 - 327
(2007/10/02)
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- REDUCTIVE ISOMERIZATION OF HALOGEN DERIVATIVES OF 2,2-DIARYLETHANES
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The mono-, di-, and trichloro derivatives of gem-diarylethanes are reduced with good yields by triethylsilane in the presence of small amounts of aluminum chloride with rearrangement and the formation of the corresponding dibenzyl derivatives.
- Parnes, Z. N.,Romanova, V. S.,Vol'pin, M. E.
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p. 968 - 971
(2007/10/02)
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- Use of Relative Counterion Type Micelles for the Determination of Selectivity Coefficients
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Monovalent/monovalent and divalent/monovalent ion exchange in hexadecyltrimethylammonium hydroxide (CTAOH), a relative counterion type micelle, was investigate by using as a probe the dehydroshlorination reactions of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD).Selectivity coefficients for the ion exchange of bromide, chloride, fluoride, nitrate, acetate, sulfate, and carbonate anions with the reactive counterion (OH-) and between the anions themselves were evaluated from the kinetic treatment of the data using a simple pseudophase ion-exchange-type formalism.
- Nascimento, Maria da Graca,Miranda, Sebastiao A. F.,Nome, Faruk
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p. 3366 - 3368
(2007/10/02)
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- SYNTHESIS OF BENZOPHENONE-4,4'-DISULFONYL CHLORIDE
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Benzophenone-4.4'-disulfonyl chloride was synthesized from 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, diphenylmethane-4,4'-disulfonyl chloride, or 1,1-dichloro-2,2-diphenylethene-4,4'-disulfonyl chloride by a series of consecutive reactions.
- Yanota, Kh.,Alov, E. M.,Moskvichev, Yu. A.,Mironov, G. S.
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p. 329 - 331
(2007/10/02)
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- Potassium Acetate-Dimethylformamide, a Selective Reagent for Dehydrohalogenation of a 1,1,1-Trichloroethyl Group and its Conversion into a 1,1-Dichlorovinyl Moiety
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Potassium acetate-dimethylformamide has been found to be a selective reagent for the mono-dehydrochlorination of the 1,1,1-trichloroethyl group and its conversion into a 1,1-dichlorovinyl moiety: the CCl4-adducts 4-6 (derived from the terminal olefinic compounds 1-3 respectively) generate the dichlorovinyl derivatives 7-9.This reagent also dehydrochlorinates DDT (10) into its xenobiotic product DDE 11.
- Reddy, R. Thimma,Nayak, U. R.
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p. 661 - 662
(2007/10/02)
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- Kinetic Behavior of Cetyltrimethylammonium Hydroxyde. The Dehydrochlorination of 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane and Some of Its Derivatives.
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The dehydrochlorination of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD), and 1-chloro-2,2-bis(p-chlorophenyl)ethane (DDM) with hydroxide ion was studied in the presence of hexadecyltrimethylammonium hydroxide (CTAOH) micelles at 25.0 deg C.The experimental results clearly deviate from the theoretical behavior expected by the pseudophase-ion-exchange model and can be explained by considering an additional reaction pathway across the micellar boundary.This additional reaction pathway in which hydroxide ion in the aqueous phase reacts directly with the organic substrate in the micelle is probably of a phase-transfer catalysis type.
- Stadler, Eduardo,Zanette, Dino,Rezende, Marcos C.,Nome, Faruk
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p. 1892 - 1896
(2007/10/02)
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- Oxygenation by Superoxide Ion of CCl4, FCCl3, HCCl3, p,p'-DDT, and Related Trichloromethyl Substrates (RCCl3) in Aprotic Solvents
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In dimethylformamide (DMF) superoxide ion (O2-) oxygenates compounds with the trichloromethyl group: CCl4, HCCl3, and FCCl3 yield bicarbonate ion; PhCCl3 yields a mixture of PhC(O)OO- and PhC(O)O-; CF3CCl3 and HOCH2CCl3 give their carboxylate anions, RC(O)O-; and p,p'-DDT yields its dechlorinated product, DDE, which in turn reacts with O2- to give (p-ClPh)2C=O.Alkyl trichloromethyl compounds are unreactive within a 10-min reaction time at millimolar concentrations.The relative rates of reaction have been measured by the rotated ring-disc voltammetric method.On the basis of the relationship between the relative reaction rates and the electrophilic character of the substrates, as measured by the peak reduction potentials (Ep), the initial step is believed to be an electron transfer from the nucleophile to the electrophilic trichloromethyl group (a nucleophilic attack on chlorine with a concerted reductive displacement of Cl- and formation of RCCl2OO*).
- Roberts, Julian L.,Calderwood, Thomas S.,Sawyer, Donald T.
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p. 7691 - 7696
(2007/10/02)
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- Effect of Normal and Functional Micelles in Elimination Reactions of Polyhalogenated Pesticides
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The dehydrochlorination of pesticides of the DDT family in the presence of functional and cationic micelles has been studied.Catalytic factors of (2 620+/-504), (2 190+/-404), and (1 470+/-215)-fold were observed for 1,1,1-trichloro-2,2-bis-(p-chlorophenyl)ethane (DDT), 1,1-dichloro-2,2-bis-(p-chlorophenyl)ethane (DDD), and 1-chloro-2,2-bis-(p-chlorophenyl)ethane (DDM) respectively, when hexadecyldimethyl-(2-hydroxyethyl)ammonium bromide (CHEDAB) was used as catalyst.Hexadecyltrimethylammonium bromide (CTAB) also showed catalytic effects (417+/-77), (208+/-40), and (70+/-14)-fold increases for DDT, DDD, and DDM, respectively, though smaller than those observed with CHEDAB.The higher catalytic activities of CHEDAB are explained in terms of the participation of the alkoxide moiety.
- Rezende, Marcos Caroli,Rubira, Adley Forti,Franco, Cesar,Nome, Faruk
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p. 1075 - 1078
(2007/10/02)
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- SUPEROXIDE-MEDIATED DEHYDROHALOGENATION REACTIONS OF THE PYRETHROID PERMETHRIN AND OTHER CHLORINATED PESTICIDES
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Superoxide generated in DMF readily converts the dihalovinyl group of permethrin and related compounds to a haloethynyl moiety and yields major products from elimination reactions of DDT, cis-chlordane, and 1,2-dibromo-3-chloropropane (DBCP).
- Dureja, Prem,Casida, John E.,Ruzo, Luis O.
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p. 5003 - 5004
(2007/10/02)
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- Limitations of the Pseudophase Model of Micellar Catalysis. The Dehydrochlorination of 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane and Some of Its Derivatives
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The dehydrochlorination of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD), and 1-chloro-2,2-bis(p-chlorophenyl)ethane (DDM) with hydroxide ion was studied in the presence of hexadecyltrimethylammonium bromide (CTAB) micelles at 25.0 deg C.The experimental results indicate that there is good agreement between the experimental results and theoretical models of micellar catalysis for (OH) in the range of 1E-3-1E-2 M.For (OH) values higher than 1E-2 M, the pseudophase model fails there is a significant deviation between the theoretically calculated and observed values of the pseudo-first-order rate constant.The experimental results can be explained by considering an additional reaction pathway across the micellar boundary, in which hydroxide ion in the aqueous phase reacts directly with the organic substrate in the micelle.This additional reaction pathway is probably of a phase transfer catalysis type.
- Nome, Faruk,Rubira, Adley F.,Franco, Cesar,Ionescu, Lavinel G.
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p. 1881 - 1885
(2007/10/02)
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- SOLVENT DEUTERIUM ISOTOPE EFFECTS ON THE RATES OF DEHYDROCHLORINATION OF DDT AND DDD BY ALKOXIDE BASES IN ALCOHOLS
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Solvent isotope effects are reported for the dehydrochlorination reactions of 2,2-di(p-chlorophenyl)1,1,1-trichloroethane (DDT) and 2,2-di(p-chlorophenyl)1,1-dichloroethane (DDD) by methoxide-methanol-d and ethoxide-ethanol-d.DDT shows large effects, kROD/kROH ca. 2, whereas DDD gives a ratio much closer to unity.These solvent isotope effects are discussed in relation to the mechanisms of the reactions, determined by other methods.
- Jarczewski, Arnold,Schroeder, Grzegorz,Leffek, K. T.
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p. 521 - 525
(2007/10/02)
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- SYNTHESIS AND REACTIVITY OF DISULFONYL CHLORIDES FROM 1,1,1-TRICHLORO-2,2-BIS(4-CHLOROPHENYL)ETHANE
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The corresponding disulfonyl chlorides, sodium disulfonates, and disulfonamides were obtained from 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane and its analogs by successive chlorosulfonation, hydrolysis, salting out, and ammonolysis.
- Novakovski, E.
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p. 1319 - 1322
(2007/10/02)
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- PULSE MICROREACTOR PESTICIDES HYDRODECHLORINATION
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Catalytic hydrodechlorination of chlorinated pesticides and other environmentally chlorinated materials into lower chlorine content compounds has been studied in a pulse microreactor .Chlorine can be catalytically removed and replaced by hydrogen to prduce partially chlorinated intermediates as well as completely dechlorinated hydrocarbons.Intermediates are equivalent to some of those obtained by natural degradation.The pulse microreactor is a simple technique to predict both product composition and reaction severity required for laboratory scale preparation of such degradation products.
- Weiss, A. H.,LaPierre, R. B.
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p. 111 - 122
(2007/10/02)
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