Synthesis of Polychloroalkanes

Nikiforov, Vladimir

doi:10.1007/698_2009_40

Cited by 7 publications

(6 citation statements)

References 59 publications

(115 reference statements)

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“…Chlorinated paraffins (CPs) are high-production volume chemicals used in various industries as plasticizers, high-pressure lubricants, or flame retardants. − Depending on the desired properties, different alkane feedstocks are chlorinated to a specific degree . CPs are commonly differentiated by alkyl chain lengths into three main groups: short-chain chlorinated paraffins (SCCPs, C 10 - to C 13 -alkanes, 40–70% chlorine), medium-chain chlorinated paraffins (MCCPs, C 14 - to C 17 -alkanes, 40–70% chlorine), and long-chain chlorinated paraffins (LCCPs, C >17 -alkanes, chlorination degree varies widely).…”

Section: Introductionmentioning

confidence: 99%

“…1−3 Depending on the desired properties, different alkane feedstocks are chlorinated to a specific degree. 4 CPs are commonly differentiated by alkyl chain lengths into three main groups: short-chain chlorinated paraffins (SCCPs, C 10 -to C 13 -alkanes, 40−70% chlorine 5 ), medium-chain chlorinated paraffins (MCCPs, C 14 -to C 17alkanes, 40−70% chlorine 6 ), and long-chain chlorinated paraffins (LCCPs, C >17 -alkanes, chlorination degree varies widely). Irrespective of the category, each technical CP product is composed of several thousand homologues (i.e., compounds of the same molecular formula, named in the following as C x Cl y ), without any predominant compound and little knowledge about individual structures.…”

Section: Introductionmentioning

confidence: 99%

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Addressing Main Challenges Regarding Short- and Medium-Chain Chlorinated Paraffin Analysis Using GC/ECNI-MS and LC/ESI-MS Methods

Mézière

Krätschmer

Pērkons³

et al. 2020

J. Am. Soc. Mass Spectrom.

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The risk assessment of chlorinated paraffins (CPs), chemicals of widespread industrial use, is struggling without standardized analytical methods to obtain reliable occurrence data. Indeed, scientists face analytical challenges that hinder the comparability of analytical methods, among them uncontrolled ionization efficiency and lack of quantification standards. In this study, our goal was to investigate potential issues faced when comparing data from different mass spectrometry platforms and quantification methods. First, the injection of the same set of singlechain length standards in three different instrumental mass spectrometry set-ups (liquid chromatography−electrospray-Orbitrap (LC/ESI-HRMS), liquid chromatography−electrospray-time-offlight (LC/ESI-MS), and gas chromatography−electron capture negative ion-Orbitrap (GC/ECNI-HRMS)) revealed a shift of homologue response patterns even in-between LC/ESI-based set-ups, which was more pronounced for CPs of low chlorination degree. This finding emphasizes the need for a comprehensive description of instrument parameters when publishing occurrence data. Second, the quantification of a data set of samples with four quantification methods showed that quantification at the sum SCCP and MCCP levels presented good comparability, while quantification at the homologue level remained unsatisfactory. In light of those results, we suggest that (i) response pattern comparison should only be performed between similar instrumental set-ups, (ii) experimental chlorination degrees should be used when quantifying according to the %Cl (instead of those provided by the suppliers), and (iii) concentration results should be expressed as the sum of SCCPs and MCCPs primarily, with an indication on the match between samples and quantification standards (for example their chlorine content).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Addressing Main Challenges Regarding Short- and Medium-Chain Chlorinated Paraffin Analysis Using GC/ECNI-MS and LC/ESI-MS Methods

Mézière

Krätschmer

Pērkons³

et al. 2020

J. Am. Soc. Mass Spectrom.

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“…1,2,9,10-tetrachlorodecane (TCD) (50.6 % Cl), 1,2,5,6,9,10-hexachlorodecane (HCD) (61.0 % Cl), and 1,2,11,12-tetrachlorododecane (TCDod) (46.0 % Cl) were chosen as representative SCCPs due to their varying degrees of chlorination and carbon chain length, as well as the commercial availability of their diene and triene precursors: 1,9-decadiene, 1,5,9-decatriene, and 1,11-dodecadiene (Combi-Blocks Inc.; San Diego, CA). Chlorination of the double bonds was achieved using sulfuryl chloride (SO2Cl2; Sigma-Aldrich) as a chlorine source and 2,2'-azobis(2-6 methylpropionitrile) (AIBN; Sigma-Aldrich) as a radical initiator 4, 58,59 ( Figure S1 in Supporting Information). Further details on the synthesis procedure are provided in the Supporting Information (SI).…”

Section: Methodsmentioning

confidence: 99%

Photochemical Degradation of Short-Chain Chlorinated Paraffins in Aqueous Solution by Hydrated Electrons and Hydroxyl Radicals

DiMento¹,

Tusei²,

Aeppli³

2020

Preprint

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Short-chain chlorinated paraffins (SCCPs) are a complex mixture of polychlorinated alkanes (C10-C13, chlorine content 40-70%). While these compounds are categorized as persistent organic pollutants, there are knowledge gaps about their environmental degradation, particularly the effectiveness and mechanism of photochemical degradation in surface waters. Photochemically-produced hydrated electrons (e-(aq)) have been shown to degrade highly chlorinated compounds in environmentally-relevant conditions more effectively than hydroxyl radicals (·OH), which can degrade a wide range of organic pollutants. This study aimed to evaluate the potential for e-(aq) to degrade SCCPs, and compare this reaction to ·OH-mediated degradation. To this end, the degradation of SCCP model compounds was investigated under laboratory conditions that photochemically produced e-(aq) or ·OH. Resulting SCCP degradation rate constants for e-(aq) were on the same order of magnitude as well-known chlorinated pesticides. Experiments in the presence of ·OH yielded similar or higher second-order rate constants. By compiling literature data for a wide range of chlorinated compounds, it was found that higher chlorine content results in higher rate constants for e-(aq) and lower for ·OH. Above a composition of approximately 60 % Cl, the e-(aq) second-order rate constants were higher than rate constants for ·OH reactions. The results of this study imply that SCCPs are susceptible to photochemical degradation in the environment, facilitated by dissolved organic matter and other sources of reactive intermediates in sunlit surface waters.

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“…This chlorination reaction shows low positional selectivity and produces many congeners and isomers and does not discriminate between stereoisomers. 8 CP mixtures can therefore comprise thousands of congeners with differing chain lengths and chlorination patterns. Currently, due to the complexity of CP mixtures and the lack of analytical standards, no analytical methods are available for the identification of individual congeners in CP mixtures or any samples contaminated with CPs.…”

Section: Introductionmentioning

confidence: 99%

Congener-Specific Partition Properties of Chlorinated Paraffins Evaluated with COSMOtherm and Gas Chromatographic Retention Indices

Hammer

Matsukami²,

Endo³

2020

Preprint

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Chlorinated Paraffins (CPs) are high volume production chemicals and have been found in various organisms including humans and in environmental samples from remote regions. It is thus of great importance to understand the physical-chemical properties of CPs. In this study, gas chromatographic (GC) retention indexes (RIs) of 26 CP congeners were measured on various polar and nonpolar columns to investigate the relationships between the molecular structure and the partition properties. Retention measurements show that analytical standards of individual CPs often contain several stereoisomers. RI values show that chlorination pattern have a large influence on the polarity of CPs. Single Cl substitutions (-CHCl-, -CH2Cl) generally increase polarity of CPs. However, many consecutive -CHCl- units (e.g., 1,2,3,4,5,6-C11Cl6) increase polarity less than expected from the total number of -CHCl- units. Polyparameter linear free energy relationship descriptors show that polarity difference between CP congeners can be explained by the H-bond donating properties of CPs. RI values of CP congeners were predicted using the quantum chemically based prediction tool COSMOthermX. Predicted RI values correlate well with the experimental data (R2, 0.975–0.995), indicating that COSMOthermX can be used to accurately predict the retention of CP congeners on GC columns.

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Synthesis of Polychloroalkanes

Cited by 7 publications

References 59 publications

Addressing Main Challenges Regarding Short- and Medium-Chain Chlorinated Paraffin Analysis Using GC/ECNI-MS and LC/ESI-MS Methods

Addressing Main Challenges Regarding Short- and Medium-Chain Chlorinated Paraffin Analysis Using GC/ECNI-MS and LC/ESI-MS Methods

Photochemical Degradation of Short-Chain Chlorinated Paraffins in Aqueous Solution by Hydrated Electrons and Hydroxyl Radicals

Congener-Specific Partition Properties of Chlorinated Paraffins Evaluated with COSMOtherm and Gas Chromatographic Retention Indices

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