Formation and Evaluation of Derivatives, Preparation and Insecticidal Evaluation of Alcoholic Analogs of Kepone

Gilbert, Everett E.; Lombardo, Pasquale; Rumanowski, E. J.; Walker, Gene

doi:10.1021/jf60144a004

Cited by 20 publications

(12 citation statements)

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“…In view of the high level of hydration in chlordecone and congeners, we first examined the possible relationship between the hydration constant of the carbonyl substrates and their ability to be spontaneously reduced. Even if we could show a trend among the carbonyl compounds possessing electron-withdrawing substituents (Cl and F atoms, Figure S5) and known to be mainly present in the gem-diol form, − this parameter could not explain the overall phenomenon. It means that the chemical reductive sulfidation is not very sensitive to the thermodynamics of the hydration reaction (Figure D).…”

Section: Resultsmentioning

confidence: 82%

“…To simplify the monitoring of bacterial and chemical reactions, we targeted volatile substrates easily detected using the gas chromatography coupled to mass spectrometry (GC-MS) technique (Figure ). According to the structural and electronic particularities of chlordecone ( 12a ), we selected a series of aldehydes and ketones containing electron-withdrawing groups ( 1a – 2a , 13a – 15a ) (known to be partially or completely hydrated) − and several cyclic ketones to explore the possible effect of the ring constraints ( 20a – 28a ). Finally, we added aliphatic, conjugated, and aromatic aldehydes and ketones to enlarge the structural diversity ( 3a – 11a , 16a – 19a ).…”

Section: Resultsmentioning

confidence: 99%

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Microbiological versus Chemical Reductive Sulfidation: An Experimental and Theoretical Study

et al. 2021

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Microbiological reductive sulfidation (RS) has rarely been documented, although it represents an efficient strategy for thiol formation. In this work, we reported on the sulfate-respiring bacterium Desulfovibrio sp.86 that has previously demonstrated RS activity toward the pesticide chlordecone. The purpose of this study was to assess its substrate versatility using a set of 28 carbonyls, to compare with chemical RS and to rationalize the observed trends using a dual experimental and theoretical approach. The chemical RS generally proceeds in two steps (S/O exchange using a sulfur donor like P4S10, reduction of the thione intermediate). Intriguingly, chlordecone was found to be converted into chlordecthiol following the first step. Hence, we designed a protocol and applied it to the 28 substrates to assess their propensity to be directly converted into thiols with the P4S10 treatment alone. Finally, we performed density functional theory calculations on these carbonyls and their thiocarbonyl derivatives to build a set of structural, electronic, and thermodynamic parameters. The results showed that chemical and microbiological RS probably involved two distinct mechanisms. Chemically, we observed that several carbonyls, possessing electron-withdrawing groups and/or aromatic rings, were directly transformed into thiols in the presence of P4S10. The correlation obtained with the electron affinity of the thiones led us to conclude that a probable single-electron reductive transfer occurred during the first step. We also found that Desulfovibrio sp.86 transformed a variety of aldehydes and ketones, without ever detecting thiones. No significant correlation was observed with the calculated parameters, but a relationship between aldehyde RS biotransformation and bacterial growth was observed. Differences in selectivity with chemical RS open the way for further applications in organic synthesis.

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Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Microbiological versus Chemical Reductive Sulfidation: An Experimental and Theoretical Study

et al. 2021

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“…Mirex (C 12 Cl 12 ) differs from chlordecone, as it possesses a dichloromethylene group in place of carbonyl moiety. Kelevan (C 17 H 12 Cl 10 O 4 ) used in Europe to fight against the Colorado potato beetle is made from chlordecone by addition of ethyl levulinate onto the ketone function (Gilbert et al, 1966). Both compounds are known to generate chlordecone among other degradative metabolites in environmental conditions (Le Déault and Procaccia, 2009).…”

Section: Introductionmentioning

confidence: 99%

Microbial Degradation of a Recalcitrant Pesticide: Chlordecone

et al. 2016

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Chlordecone (Kepone®) is a synthetic organochlorine insecticide (C10Cl10O) used worldwide mostly during the 1970 and 1980s. Its intensive application in the French West Indies to control the banana black weevil Cosmopolites sordidus led to a massive environmental pollution. Persistence of chlordecone in soils and water for numerous decades even centuries causes global public health and socio-economic concerns. In order to investigate the biodegradability of chlordecone, microbial enrichment cultures from soils contaminated by chlordecone or other organochlorines and from sludge of a wastewater treatment plant have been conducted. Different experimental procedures including original microcosms were carried out anaerobically over long periods of time. GC-MS monitoring resulted in the detection of chlorinated derivatives in several cultures, consistent with chlordecone biotransformation. More interestingly, disappearance of chlordecone (50 μg/mL) in two bacterial consortia was concomitant with the accumulation of a major metabolite of formula C9Cl5H3 (named B1) as well as two minor metabolites C10Cl9HO (named A1) and C9Cl4H4 (named B3). Finally, we report the isolation and the complete genomic sequences of two new Citrobacter isolates, closely related to Citrobacter amalonaticus, and that were capable of reproducing chlordecone transformation. Further characterization of these Citrobacter strains should yield deeper insights into the mechanisms involved in this transformation process.

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“…T HE electropositive nature of the carbonyl carbon atom in the perchlorinated caged ketone (I), decachlorooctahydro-1, 3, 4-metheno -2fí-cyclobuta [cd] pentalen-2-one, also known as decachloropentacyclo [5.3.0.02,6.04,1°.05'9] decan-3one, or as Kepone, has already been demonstrated by its ability to form adducts with alcohols or amines, (4) and to undergo uncatalyzed condensation with aliphatic ketones and other compounds containing activated methylene groups (3). The purpose of this study was to determine the ease of reactivity of the carbonyl group of I with various aromatic nuclei, as follows:…”

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confidence: 99%

“…"Demethylated to Ila; also proved identical with material made by the Grignard reaction. reaction of I with Grignard reagents from 4-and 2-bromoanisoles, respectively, followed by demethylation in each case (3). N.M.R.…”

mentioning

confidence: 99%

Perhaloketones. Aromatic Derivatives of a Perchlorinated Caged Ketone.

Farah¹,

Gilbert²,

Lombardo³

et al. 1966

J. Chem. Eng. Data

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The perchlorinated cage ketone, decachloropentacyclo [5.3.0.02,6.O4,10 3.059 ] decan-3-one, (I) has been reacted with various aromatic compounds-mainly phenols and hydrocarbons-using several acid catalysts. Tertiary carbinols (II) were prepared from phenols, and "bis" compounds (III) were obtained from phenols and the other aromatic compounds. The carbonyl carbon atom in I is concluded to be less electropositive than that in the fluorinated acetones. A number of secondary derivatives were also prepared from the aromatic condensates of I.

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Formation and Evaluation of Derivatives, Preparation and Insecticidal Evaluation of Alcoholic Analogs of Kepone

Cited by 20 publications

References 0 publications

Microbiological versus Chemical Reductive Sulfidation: An Experimental and Theoretical Study

Microbiological versus Chemical Reductive Sulfidation: An Experimental and Theoretical Study

Microbial Degradation of a Recalcitrant Pesticide: Chlordecone

Perhaloketones. Aromatic Derivatives of a Perchlorinated Caged Ketone.

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