Chlorine Source Research Articles

Factors Influencing the Palladium‐Catalyzed Asymmetric Synthesis of α‐Chloromethylene‐γ‐butyrolactones

Abstractα‐Methylene‐γ‐butyrolactone is an important skeleton in many natural products and pharmaceuticals. The factors influencing the palladium‐catalyzed asymmetric synthesis of α‐chloromethylene‐γ‐butyrolactones were investigated, including ligands, additives, the chlorine source, temperature, and solvents. We found that the reaction had broad substrate scope for the synthesis of the corresponding chiral products when the ligand, chlorine source and additives were optimized. The results will improve the catalytic synthesis of chiral α‐chloromethylene‐γ‐butyrolactones.

Measurements and Modeling of the Interhemispheric Differences of Atmospheric Chlorinated Very Short‐Lived Substances

AbstractChlorinated very short‐lived substances (Cl‐VSLS) are ubiquitous in the troposphere and can contribute to the stratospheric chlorine budget. In this study, we present measurements of atmospheric dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), chloroform (CHCl3), and 1,2‐dichloroethane (1,2‐DCA) obtained during the National Aeronautics and Space Administration (NASA) Atmospheric Tomography (ATom) global‐scale aircraft mission (2016–2018), and use the Community Earth System Model (CESM) updated with recent chlorine chemistry to further investigate their global tropospheric distribution. The measured global average Cl‐VSLS mixing ratios, from 0.2 to 13 km altitude, were 46.6 ppt (CH2Cl2), 9.6 ppt (CHCl3), 7.8 ppt (1,2‐DCA), and 0.84 ppt (C2Cl4) measured by the NSF NCAR Trace Organic Analyzer (TOGA) during ATom. Both measurements and model show distinct hemispheric gradients with the mean measured Northern to Southern Hemisphere (NH/SH) ratio of 2 or greater for all four Cl‐VSLS. In addition, the TOGA profiles over the NH mid‐latitudes showed general enhancements in the Pacific basin compared to the Atlantic basin, with up to ∼18 ppt difference for CH2Cl2 in the mid troposphere. We tagged regional source emissions of CH2Cl2 and C2Cl4 in the model and found that Asian emissions dominate the global distributions of these species both at the surface (950 hPa) and at high altitudes (150 hPa). Overall, our results confirm relatively high mixing ratios of Cl‐VSLS in the UTLS region and show that the CESM model does a reasonable job of simulating their global abundance but we also note the uncertainties with Cl‐VSLS emissions and active chlorine sources in the model. These findings will be used to validate future emission inventories and to investigate the fast convective transport of Cl‐VSLS to the UTLS region and their impact on stratospheric ozone.

Catalytic Enantioselective Nucleophilic α-Chlorination of Ketones with NaCl.

Catalytic enantioselective α-chlorination of ketones is a highly desirable process. Different from the conventional approaches that employ corrosive electrophilic chlorination reagents, the process disclosed here employs nucleophilic chloride, aqueous NaCl solution, and even seawater, as green inexpensive chlorine sources. This mechanistically distinct and electronically opposite approach provides facile access to diverse highly enantioenriched acyclic α-chloro ketones that are less straightforward by conventional approaches. With a chiral thiourea catalyst, a range of racemic α-keto sulfonium salts underwent enantioconvergent carbon-chlorine bond formation with high efficiency and excellent enantioselectivity under mild conditions. The sulfonium motif plays a crucial triple role by permitting smooth dynamic kinetic resolution to take place via a chiral anion binding mechanism in a well-designed phase-transfer system. This protocol represents a new general platform for the asymmetric nucleophilic α-functionalization of carbonyl compounds.

Scalable catalyst free electrochemical chlorination of aminophenol derivatives enabled by a quasi-divided cell approach

Chlorination of 4-aminophenol derivatives can be performed using DCM as the solvent and the chlorine source using a parallel plate flow “quasi-divided” cell reactor.

Visible light-induced FeCl3-catalyzed chlorination of C–H bonds with MgCl2

Visible light-promoted C(sp3)–H bond chlorination with MgCl2 as a chlorine source in AcOH/CH3CN in the presence of FeCl3 is reported.

C3-Chlorination of C2-substituted benzo[b]thiophene derivatives in the presence of sodium hypochlorite.

Benzo[b]thiophene rings are common synthons for the development of novel drugs and materials, and thus, the discovery of facile ways for their functionalization is of value. In this work, a new method for the C3-chlorination of C2-substituted benzothiophene derivatives is described. The chlorine source is sodium hypochlorite pentahydrate (NaOCl·5H2O), and optimal transformations occur in aqueous acetonitrile at 65-75 °C to provide the corresponding C3-halogenated products in variable yields (30-65%). The reaction occurs in the presence of vinyl and alkyl groups, while the presence of alcohols leads to competing oxidation reactions at the heterobenzylic position. The presence of a carbonyl group at the C2-position inhibited the halogenation reaction, while the use of benzofuran led to a highly exothermic reaction, presumably via the formation of a peroxide intermediate. Reactions carried out at lower temperatures led to side reactions associated with competing oxidative processes. To gain a better understanding of the mechanism of the reaction, DFT calculations were carried out, where the heteroatom enables the formation of a hypochlorous acidium ion that serves to generate a C2-C3 chloronium ion intermediate in a step-wise manner, which in turn leads to the formation of an S-stabilized C2-carbocation that undergoes re-aromatization to the corresponding C3-chlorinated products. To probe potential synthetic applications, a model C3-chloro derivative was coupled with phenylboronic acid using standard Suzuki-Miyaura coupling conditions.

Additive-free oxychlorination of unsaturated C-C bonds with tert-butyl hypochlorite and water.

Herein we report an additive-free protocol for the facile synthesis of α,α-dichloroketones and α-chlorohydrins from various aryl terminal, diaryl internal, and aliphatic terminal alkynes and alkenes, respectively. The commercially available tert-butyl hypochlorite (tBuOCl) was employed as a suitable chlorinating reagent, being accompanied by the less harmful tBuOH as the by-product. In addition, the oxygen atoms in the products came from water rather than molecular oxygen, based on the 18O-labelling experiments. Meanwhile, the diastereoselectivity of the Z- and the corresponding E-alkenes has been compared and rationalized. Using a group of control experiments, the possible mechanisms have been proposed as the initial electrophilic chlorination of unsaturated C-C bonds in a Markovnikov-addition manner in general followed by a nucleophilic addition with water. This work simplified the oxychlorination method with a mild chlorine source and a green oxygen source under ambient conditions.

POCl3/Sulfoxide-Promoted Synthesis of Indolizino[8,7-b]indoles.

A mild chlorocyclization of pyrrole-tethered indoles has been realized using POCl3 as the chlorine source and tetramethylene sulfoxide as the promoter. A variety of chlorinated indolizino[8,7-b]indole derivatives have been constructed efficiently under this reaction system in moderate to good yields (19 examples, up to 93% yield).

Light‐induced FeCl3‐catalyzed selective benzyl C−H chlorination with trifluoromethanesulfonyl chloride

AbstractHere we report a light‐induced FeCl3‐catalyzed approach for benzyl C−H chlorination with remarkable regioselectivity, which enables alkylbenzenes to be converted into versatile benzyl chlorides under mild conditions using trifluoromethanesulfonyl chloride (TfCl) as the chlorine source. DFT calculations show that the dynamics preference of benzylic α−C−H chlorination is more pronounced by employing TfCl.

Codisposal of landfill leachate concentrate and antimony mine soils using a one-part geopolymer system for cationic and anionic heavy metals immobilization

Geopolymer solidification/stabilization technology has developed rapidly in the remediation field of heavy metal-contaminated soil. However, geopolymers exhibit low anionic heavy metal immobilization efficiency due to their electronegativity and alkali activation characteristics. This study constructed a one-part blast furnace slag-based geopolymer system using landfill leachate concentrate (LLC) as chlorine and humic acid sources and achieved the solidification/stabilization of cations (Cd, Cu, Hg, and Pb) and anions (Sb and As) in the antimony mine soils (AMS). The LLC addition increased the Sb and As fixation rates from 92%∼94% and 82∼86%, respectively, to over 99%, reducing the leaching concentration of all heavy metal ions to the ppb level. LLC improved the chemical stability and physical encapsulation of Sb/As in three ways: inducing a Friedel’s salt (FS) formation, enhancing humic acid complexation/chelation, and promoting geopolymerization. Wet curing was more conducive to FS formation in the geopolymer than dry curing and increased the 28-day compressive strength by 38.5%. Due to the SiO2 skeleton support effect in AMS, a 30 wt% AMS addition was beneficial for geopolymer strength development. Our study provided a harmless method for the codisposal of LLC and AMS and improved the efficiency of geopolymer fixation of complex heavy metal cations and anions.

High Chlorine Concentrations in an Unconventional Oil and Gas Development Region and Impacts on Atmospheric Chemistry.

Growth in unconventional oil and gas development (UOGD) in the United States has increased airborne emissions, raising environmental and human health concerns. To assess the potential impacts on air quality, we deployed instrumentation in Karnes City, Texas, a rural area in the middle of the Eagle Ford Shale. We measured several episodes of elevated Cl2 levels, reaching maximum hourly averages of 800 ppt, the highest inland Cl2 concentration reported to date. Concentrations peak during the day, suggesting a strong local source (given the short photolysis lifetime of Cl2) and/or a photoinitiated production mechanism. Well preproduction activity near the measurement site is a plausible source of these high Cl2 levels via direct emission and photoactive chemistry. ClNO2 is also observed, but it peaks overnight, consistent with well-known nocturnal formation processes. Observations of organochlorines in the gas and particle phases reflect the contribution of chlorine chemistry to the formation of secondary pollutants in the area. Box modeling results suggest that the formation of ozone at this location is influenced by chlorine chemistry. These results suggest that UOGD can be an important source of reactive chlorine in the atmosphere, impacting radical budgets and the formation of secondary pollutants in these regions.

Copper(I)‐Catalyzed Interrupted Click Reaction: Synthesis of 1,4,5‐Trisubstituted 5‐Chloro‐1,2,3‐Triazoles

Abstract5‐Halo‐1,2,3‐triazoles are important scaffolds in organic chemistry, but current click reactions cannot produce 1,4,5‐trisubstituted 5‐chloro‐1,2,3‐triazoles in a simple way. Herein, we disclosed a Cu(I)‐catalyzed interrupted click reaction, using N‐chlorophthalimide as an electrophilic chlorine source, enabling the facile synthesis of 1,4,5‐trisubstituted 5‐chloro‐1,2,3‐triazoles in one step from readily available terminal alkynes and azides. Complete control of regioselectivities with a broad substrate scope was accomplished by this approach. Furthermore, a novel epoxidation was developed using 5‐chloro‐triazole as substrate, which could be further applied in various organic transformations.

POCl3/Sulfoxide and AcCl/Sulfoxide Mediated Chlorination of Pyrrolo[2,1-a]isoquinolines.

We have developed an efficient chlorination of pyrrolo[2,1-a]isoquinoline derivatives using POCl3 as the chlorine source and tetramethylene sulfoxide as a promoter. A series of pyrrolo[2,1-a]isoquinolines, polysubstituted pyrroles, and naphthols have been readily chlorinated under mild reaction conditions (26 examples, up to >99% yield). AcCl can also act as the chlorine source competently in this chlorination reaction.

Molecular Insights into the Spontaneous Generation of Cl2O in the Reaction of ClONO2 and HOCl at the Air-Water Interface.

Chemical processes involving chlorine nitrate (ClONO2) at the surface of stratospheric aerosols are crucial to ozone depletion. Herein, we show a reaction route for the formation of Cl2O, which is a source of stratospheric chlorine, in the ClONO2 + HOCl reaction at the air-water interface. Our ab initio molecular dynamics (AIMD) simulations show that the (ClONO2)Cl···O(HOCl) halogen bond plays a key role in the reaction and is the main interaction between ClONO2 and HOCl both at the air-water interface and in the bulk liquid water. Furthermore, metadynamics-based AIMD simulations reveal two pathways: (i) The OCl fragment of HOCl binds to the Cl atom in ClONO2, resulting in the formation of Cl2O and NO3-. Simultaneously, the remaining hydrogen atom is transferred to a water molecule to form H3O+. (ii) HOCl acts as a bridge for Cl atom transfer from ClONO2 to the O atom of a water molecule, and this water molecule transfers one of its H atoms to another water molecule, forming two HOCl molecules, NO3-, and H3O+. Free-energy calculations show that the former is the energetically more favorable process. More importantly, the free-energy barrier for Cl2O formation at the air-water interface is only ∼0.8 kcal/mol, and the reaction is exothermic. These findings provide insights into the importance of fundamental chlorine chemistry and the broader implications of the aerosol air-water interface for atmospheric chemistry.

CVD growth of 3C-SiC layers on 4H-SiC substrates with improved morphology

Chloride-based CVD growth of 3C-SiC epitaxial layers on on-axis 4H-SiC substrates has been studied using chloromethane and silane as precursors. Hydrogen chloride is utilized as additional chlorine source. Process parameters, such as growth temperature, C/Si ratio, Cl/Si ratio and temperature ramp-up condition, are investigated. Smooth 3C-SiC layers without DPB defects on the surface could be obtained with optimized process at a growth rate of 14 μm/h. Low temperature photoluminescence measurement shows sharp near bandgap emission, which verifies the good optical properties of the epitaxial layer. The growth window is wide in this process by using chlorinated precursors compared to the standard chemistry.

Photocatalytic chlorine atom production on mineral dust–sea spray aerosols over the North Atlantic

Active chlorine in the atmosphere is poorly constrained and so is its role in the oxidation of the potent greenhouse gas methane, causing uncertainty in global methane budgets. We propose a photocatalytic mechanism for chlorine atom production that occurs when Sahara dust mixes with sea spray aerosol. The mechanism is validated by implementation in a global atmospheric model and thereby explaining the episodic, seasonal, and location-dependent 13C depletion in CO in air samples from Barbados [J.E. Mak, G. Kra, T. Sandomenico, P. Bergamaschi, J. Geophys. Res. Atmos. 108 (2003)], which remained unexplained for decades. The production of Cl can also explain the anomaly in the CO:ethane ratio found at Cape Verde [K. A. Read et al., J. Geophys. Res. Atmos. 114 (2009)], in addition to explaining the observation of elevated HOCl [M. J. Lawler et al., Atmos. Chem. Phys. 11, 7617-7628 (2011)]. Our model finds that 3.8 Tg(Cl) y-1 is produced over the North Atlantic, making it the dominant source of chlorine in the region; globally, chlorine production increases by 41%. The shift in the methane sink budget due to the increased role of Cl means that isotope-constrained top-down models fail to allocate 12 Tg y-1 (2% of total methane emissions) to 13C-depleted biological sources such as agriculture and wetlands. Since 2014, an increase in North African dust emissions has increased the 13C isotope of atmospheric CH4, thereby partially masking a much greater decline in this isotope, which has implications for the interpretation of the drivers behind the recent increase of methane in the atmosphere.

Chloramines as an important photochemical source of chlorine atoms in the urban atmosphere

Monochloramine, dichloramine and trichloramine (NH2Cl, NHCl2, NCl3) are measured in the ambient atmosphere, in downtown Toronto in summer (median 39, 15 and 2.8 ppt) and winter (median 11, 7.3 and 0.7 ppt). NCl3 and NHCl2 were also measured in summer (median 1.3 and 14 ppt) from a suburban Toronto location. Measurements at two locations demonstrate prevalence of chloramines in an urban atmosphere. At both sites, NCl3 exhibits a strong diel pattern with maximum values during the night, and photolytic loss with sunrise. At the downtown site, a strong positive correlation between NH2Cl and NHCl2 in the summer night indicates a common source, with daily average peak mixing ratios approaching 500 and 250 ppt, respectively. As a previously unidentified source of chlorine (Cl) atoms, we demonstrate that NCl3 photolysis contributes 49 to 82% of the total local summertime Cl production rate at different times during the day with an average noontime peak of 3.8 × 105 atoms/cm3/s, with smaller contributions from ClNO2 and Cl2. Photolysis of NH2Cl and NHCl2 may augment this Cl production rate. Our measurements also demonstrate a daytime enhancement of chloroacetone in both the summer and winter, demonstrating the importance of Cl photochemistry. The results suggest that chloramines are an important source of Cl atoms in urban areas, with potential impacts on the abundance of organic compounds, ozone, nitrogen oxides, and particulate matter. Future studies should explore the vertical gradients of chloramines and their contribution to Cl production throughout the boundary layer.

Photochemical Aminochlorination of Alkenes without the Use of an External Catalyst.

The niche field of photochemistry offers opportunities that are not found in "traditional" ground state chemical pathways. Aminochlorinated derivatives are an interesting family of 1,2-difunctionalised compounds that provide access to a variety of natural products and pharmaceutical active substances. A practical, catalyst-free chloroamination protocol is described herein, providing access to intermediates of great importance, utilising mild and photochemical reaction conditions (370 nm), where N-chlorosulfonamides are used as both nitrogen and chlorine sources. A wide variety of olefins, decorated with a plethora of functional groups, was tested providing excellent results (28 examples, 18-88 % yield). Mechanistic studies (UV-Vis, control experiments and quantum yield measurement) were also performed.

Ru(phen)3 Cl2 -Catalyzed Chlorotrifluoromethylation of Unactivated Alkenes.

A novel Ru(phen)3 Cl2 -catalyzed free-radical chlorotrifluoromethylation reaction of unactivated olefins was investigated. Substituted 8-aminoquinoline-derived inert enamides were reacted with the Togni regent to afford a broad range of Cl-containing trifluoromethyl derivatives in good yields. The reaction proceeded at 90 °C and experimental result shows that the chlorine source of the products originated from LiCl.

Regio- and Stereoselective Hydrochlorination/Cyclization of 1,n-Enynes by FeCl3 Catalysis.

A highly regio- and stereoselective hydrochlorination/cyclization of enynes has been reported by FeCl3 catalysis. A variety of enynes undergo this cyclization transformation with acetic chloride as the chlorine source and H2O providing protons via a cationic pathway. This protocol provides a cheap, simple, stereospecific, and effective cyclization to afford heterocyclic alkenyl chloride compounds as Z isomers with high yields (≤98%) and regioselectivity.