Arene-chlorination using chlorinated waste

Abstract

Herein described is a method for chlorination of a substrate compound containing an aromatic moiety, in particular an arene moiety with 3 to 20 carbon atoms, wherein the substrate compound is reacted with a chlorine-donor, in particular an organic chlorine donor, in the presence of a catalyst, an oxidising agent, and a solvent. Also described is the use of a chlorine-containing compound, in particular a chlorine-containing solid or liquid organic compound, more particularly a chlorinated organic waste compound, as chlorine-donor for the chlorination of a substrate compound containing an aromatic moiety, in particular an arene moiety, with 3 to 20 carbon atoms.

Description

[0001]April 26, 2024Arene-Chlorination using Chlorinated WasteThe invention relates to a method for chlorination of a substrate compound containingan arene moiety and the use of a chlorine-containing solid or liquid organiccompound, in particular an organic waste compound, as chlorine-donor for thechlorination of arenes.BACKGROUNDChlorinated compounds are ubiquitous in industrialized societies as the physical andchemical properties of hydrocarbons are extensively modified and improvedfollowing chlorination. Thus, chlorine-containing hydrocarbons are widely used asplastics, rubbers, resins, solvents, and have applications as intermediates used in thesynthesis of agrochemicals and pharmaceuticals or are even present in agrochemicaland pharmaceutical products (see e.g. Naclerio, N. D.; Karsai, A.; Murray-Cooper, M.;Ozkan-Aydin, Y.; Aydin, E.; Goldman, D. I.; Hawkes, E. W., Sci. Robot. 2021, 6,eabe2922Jordan, A. et al., Chem. Rev. 2021, 121, 1582-1622; Bhutani, P.; Joshi, G.; Raja,N.; Bachhav, N.; Rajanna, P. K.; Bhutani, H.; Paul, A. T.; Kumar, R., J. Med. Chem. 2021,64, 2339-2381).Chlorine-containing hydrocarbons are widely used and may be persistent in theenvironment or decompose to release toxic compounds, which can accumulate in thefood chain. Exposure to chlorinated waste is even associated with suppression of theimmune system and cancer (see e.g. Z. Liew, P. Guo, Science 2022, 375, 720-721; A. L.Yee, J. A. Gilbert, Science 2016, 353, 348-349). However, methods to dispose of wastechlorine-containing hydrocarbons are currently inadequate.Chlorine-containing hydrocarbon waste is one of the most problematic types of wastefor several reasons. The common industrial approaches (landfill and incineration)lead to the formation of hazardous products including dioxins and corrosive gases, i.e.HCl and Cl2. These problems are amplified by the large amounts of chlorine-containinghydrocarbon waste. Pyrolysis and hydrocracking are also unsuitable as they result inthe same problems as industrial incineration. Disposal of chlorinated waste with lowenvironmental impact is therefore both highly desirable and highly challenging (seee.g. Martín, A. J.; Mondelli, C.; Jaydev, S. D.; Pérez-Ramírez, J., Chem 2021, 7, 1487-1533; Ellis, L. D.; Rorrer, N. A.; Sullivan, K. P.; Otto, M.; McGeehan, J. E.; Román-Leshkov, Y.; Wierckx, N.; Beckham, G. T., Nat. Catal. 2021, 4, 539-556; C. Jehanno et al.,Nature 2022, 603, 803-814). Several methods have been reported in this respect.For example, catalytic hydrocracking has been extensively investigated for upgradinga range of polymers. However, when applied to chlorinated polymers, catalystdeactivation is usually observed (see e.g. Chu, M.; Liu, Y.; Lou, X.; Zhang, Q.; Chen, J.,ACS Catal.2022, 12, 4659-4679; Lee, W.-T.; van Muyden, A.; Bobbink, F. D.; Mensi, M.D.; Carullo, J. R.; Dyson, P. J., Nat. Commun. 2022, 13, 4850; F. Zhang et al., Science2020, 370, 437-441; R. J. Conk et al., Science 2022, 377, 1561-1566).Further, a two-step process comprising dechlorination of the chlorinated wastefollowed by absorption of the resulting HCl and decomposition of the dechlorinatedhydrocarbon compound has been reported. Although this process has a reducedenvironmental impact, it is expensive and largely unviable (see e.g. A. J. Martín et al.,Chem 2021, 7, 1487-1533; Hou, Q.; Zhen, M.; Qian, H.; Nie, Y.; Bai, X.; Xia, T.; Laiq UrRehman, M.; Li, Q.; Ju, M., Cell Rep. Phys. Sci. 2021, 2, 100514).Recently an electrochemical dechlorination method was reported forpolyvinylchloride (PVC), but only partial dechlorination (< 20% conversion of the Clgroups) was achieved and the method might be difficult to upscale (see D. E. Fagnaniet al., Nat. Chem. 2022, doi.org / 10.1038 / s41557-022-01078-w). Other reporteddechlorination methods for chlorinated hydrocarbon compounds suffer from lowreaction rates and low Faradaic efficiencies (typically < 50%; see e.g. G. Gan et al., ACSHT / so 230017WO26 April 2024Catal. 2021, 11, 14284-14292; G. Gan et al., ACS Nano 2020, 14, 9929-9937; C. Choi etal., Nat. Nanotechnol. 2022).In addition to chlorinated hydrocarbon waste such as PVC tubes, waste chlorinatedsolvents are problematic with incineration being the conventional method used todispose of them as bioremediation is slow (see e.g. A. Alberini, J. Bartholomew,Contemp. Econ. Policy 1999, 17, 309-320; D. Pekelney, J. Hazard. Mater.1990, 23, 293-315).It follows from the prior art elucidated above that there is no sustainable,economically viable, and scalable method to eliminate different chlorinatedhydrocarbon wastes. Thus, it is an object of the present invention to provide a methodto eliminate chlorine waste without the formation of toxic by-products. Ideally, thehydrocarbon components are eliminated simultaneously. The method is preferablyeconomically viable and / or scalable.Other and further objects, features and advantages of the present invention willbecome apparent more fully from the following description.SUMMARY OF THE INVENTIONSome or all of these objects are achieved with the present invention by the methodaccording to claim 1 and the use according to claim 15.It was surprisingly found that in the method according to the invention chlorinatedcompounds, such as chlorinated solid and / or liquid waste streams, could be efficientlyemployed as chlorine donors in the chlorination of arene compounds. Thus, thepresent invention provides an efficient route to safely dispose of hazardouschlorinated waste by its dechlorination and conversion to CO2, CO and H2O, while theresulting chlorine compounds can be used as convenient chlorine donors for thechlorination of aromatic compounds, in particular arene compounds, to aryl chlorides.The present invention overcomes the limitations of the prior art in terms ofHT / so 230017WO26 April 2024environmentally benign disposal of chlorinated hydrocarbon waste andsimultaneously affords high-value aryl chlorides in good yields without theproduction of hazardous by-products.A range of aromatic and heteroaromatic compounds with arene moieties that have 3to 20 carbon atoms are suitable substrates for the chlorination reaction, for examplethose based on pyridine or pyrimidine moieties. Additionally, substrates withelectron-donating or -withdrawing substituents can also be chlorinated.The aromatic moiety, in particular the arene moiety, with 3 to 20 carbon atoms in thesubstrate compound preferably consists of a single aromatic or heteroaromatic ring ora fused aromatic or heteroaromatic ring system that may be substituted with non-aromatic substituents or with aromatic substituents that are not conjugated with thering or the ring system. The amount of carbon atoms preferably refers to the amountof carbon atoms within the ring or the ring system and excludes the carbon atoms ofoptional non-aromatic substituents and the aromatic substituents that are notconjugated with the ring or the ring system. For example, in 2-(p-methoxyphenyl)pyridine, there are two aromatic moieties, in particular two arenemoieties – an aromatic p-methoxyphenyl moiety having six carbon atoms connectedto a heteroaromatic pyridine moiety having five carbon atoms. In 7,8-benzoquinoline,there is only one aromatic moiety having thirteen carbon atoms. The substratecompound may also consist of the aromatic moiety, as for example in 7,8-benzoquinoline.DETAILED DESCRIPTIONThe invention provides for a method for the chlorination of a substrate compoundcontaining an aromatic moiety, in particular an arene moiety, with 3 to 20 carbonatoms in the presence of a catalyst, an oxidising agent, and a solvent, using a chlorine-donor, in particular an organic chlorine donor.HT / so 230017WO26 April 2024Further advantageous embodiments of the invention are specified in the dependentclaims and are elucidated in detail herein below.According to an embodiment, a method for the chlorination of a substrate compoundcontaining an aromatic moiety, in particular an arene moiety, with 3 to 20 carbonatoms is provided wherein the substrate compound is reacted with an organicchlorine-donor the presence of a catalyst, an oxidising agent, and a solvent.The chlorine donor may in particular be an organic chlorine donor. Various organicchlorine-containing compounds can be used as organic chlorine-donors in the methodof the present invention. According to an embodiment of the invention, the chlorine-donor contains a chlorinated hydrocarbon compound. The chlorine-donor can alsoconsist of a chlorinated hydrocarbon compound. Chlorinated hydrocarboncompounds can in particular be relatively easily handled and can be less expensivethan specialised chlorination reagents such as chloramines.The chlorine donor, in particular the organic chlorine donor, more particularly thechlorinated hydrocarbon compound, can be solid or liquid at 25 °C. This simplifies thehandling of the compounds and of the reaction mixture compared to gaseouschlorination reagents.According to a preferred embodiment, the chlorinated hydrocarbon compoundcontains a chlorine atom connected to an aliphatic moiety. Preferably, the chlorinatedhydrocarbon compound contains a tertiary alkyl chloride moiety, a secondary alkylchloride moiety, and / or a primary alkyl chloride moiety. More preferably, thechlorinated hydrocarbon compound contains a secondary alkyl chloride moiety,and / or a primary alkyl chloride moiety. Most preferably, the chlorinated hydrocarboncompound contains a primary alkyl chloride moiety. The chlorine donor, in particularthe chlorinated hydrocarbon compound, is preferably a chlorine-containing polymer,more preferably a polymer having chlorine atoms connected to carbon atoms, forexample chloride side chains such as in polyvinylchloride.HT / so 230017WO26 April 2024According to an embodiment, the chlorine-donor contains a chlorine atom connectedto a carbon atom, a nitrogen atom, a sulfur atom, or a hydrogen atom, in particularconnected to a nitrogen atom, a sulfur atom, or a hydrogen atom or to a carbon atom, anitrogen atom or a sulfur atom.According to an embodiment, the chlorine-donor is selected from the group consistingof polyvinyl chloride, polyvinylidene chloride, polyepichlorohydrin, neoprene,poly(epichlorohydrin-co-ethylene oxide), poly(epichlorohydrin-co-CO2),dichloromethane, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2-trichloroethane, 1,2-dichloroethene, perchloroethene, 1,6-dichlorohexane, 2-chlorohexane, 1,4-dichlorobutene, chlorocyclohexane, (3-chlorobutyl)benzene, benzylchloride, epichlorohydrin, epichlorohydrin carbonate, benzoyl chloride, thionylchloride, 2,4,6-trichlorophenol, 1-chloropiperidine, N-chlorosuccinimide, chloramine-T, tetrabutylammonium chloride, HCl, and mixtures thereof. The chlorine-donor mayalso be selected from the group consisting of polyvinyl chloride, polyvinylidenechloride, polyepichlorohydrin, neoprene, poly(epichlorohydrin-co-ethylene oxide),poly(epichlorohydrin-co-CO2), dichloromethane, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2-trichloroethane, 1,2-dichloroethene, perchloroethene, 1,6-dichlorohexane, 2-chlorohexane, 1,4-dichlorobutene, chlorocyclohexane, (3-chlorobutyl)benzene, benzyl chloride, epichlorohydrin, epichlorohydrin carbonate,benzoyl chloride, 2,4,6-trichlorophenol, and mixtures thereof, in particular selectedfrom the group consisting of polyvinyl chloride, polyvinylidene chloride,polyepichlorohydrin, neoprene, poly(epichlorohydrin-co-ethylene oxide),poly(epichlorohydrin-co-CO2), dichloromethane, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2-trichloroethane, 1,2-dichloroethene, perchloroethene, 1,6-dichlorohexane, 2-chlorohexane, 1,4-dichlorobutene, chlorocyclohexane, (3-chlorobutyl)benzene, benzyl chloride, epichlorohydrin, epichlorohydrin carbonate,and mixtures thereof. Preferably, the chlorine-donor is selected from the groupconsisting of polyvinyl chloride, polyvinylidene chloride, polyepichlorohydrin,neoprene, poly(epichlorohydrin-co-ethylene oxide), poly(epichlorohydrin-co-CO2),HT / so 230017WO26 April 2024dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloroethene, 1,6-dichlorohexane, 2-chlorohexane, 1,4-dichlorobutene, (3-chlorobutyl)benzene, benzylchloride, epichlorohydrin, epichlorohydrin carbonate, thionyl chloride, 2,4,6-trichlorophenol, 1-chloropiperidine, HCl, and mixtures thereof, more preferablyselected from the group consisting of polyvinyl chloride, polyvinylidene chloride,polyepichlorohydrin, neoprene, poly(epichlorohydrin-co-ethylene oxide),poly(epichlorohydrin-co-CO2), dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloroethene, 1,6-dichlorohexane, 2-chlorohexane, 1,4-dichlorobutene, (3-chlorobutyl)benzene, benzyl chloride, epichlorohydrin,epichlorohydrin carbonate, and mixtures thereof. In a particularly preferredembodiment, chlorine-donors are selected from the group consisting of polyvinylchloride, polyvinylidene chloride, dichloromethane, 1,2-dichloroethane, benzylchloride, and mixtures thereof. Most preferred is the use of polyvinyl chloride aschlorine-donor.Advantageously, the chlorine-donor can be employed in the form of chlorinatedsolvent waste or post-consumer plastic waste, such as polyvinyl chloride pipes.The chlorine-donor is advantageously employed in an amount of 1.0 to 5.0equivalents, more preferably 1.0 to 3.0 equivalents, even more preferably 1.0 to 2.0equivalents, most preferably 1.5 equivalents, based on the amount of substratecompound. The use of less than 1.0 equivalents could result in incomplete conversion,while the use of excessive amounts of chlorine-donor is disadvantageous from aneconomic perspective.In the method according to the invention, a substrate compound containing an arenemoiety is reacted with an organic chlorine-donor in the presence of a catalyst, anoxidising agent, and a solvent. Advantageously, the catalyst can be a heterogeneous orhomogeneous, preferably a homogeneous, catalyst.HT / so 230017WO26 April 2024In a preferred embodiment of the method according to the invention, the catalystcontains a metal selected from the group consisting of copper, nickel, cobalt,palladium, and mixtures thereof. More preferably the metal is copper and / orpalladium, even more preferably a palladium compound and / or a copper salt.According to an embodiment, the catalyst contains palladium, in particular apalladium compound. Preferred palladium compounds are PdO, Pd(PPh3)4, PdCl2, andmixtures thereof. According to another embodiment, the catalyst contains copper, inparticular a copper salt. Preferred copper salts are selected from the group consistingof CuCl2, CuBr2, CuI2, Cu(OAc)2, Cu(OTf)2, CuSO4, Cu(acac)2, CuPF6(CH3CN)2, CuO,and / or Cu(NO3)2, and mixtures thereof, more preferably selected from the groupconsisting of Cu(OAc)2, Cu(OTf)2, CuSO4, Cu(acac)2, CuPF6(CH3CN)2, CuO, and / orCu(NO3)2, and mixtures thereof.Thus according to an embodiment, the catalyst contains a palladium compoundand / or a copper salt selected from the group consisting of PdO, CuCl2, CuBr2, CuI2,Cu(OAc)2, Cu(Otf)2, CuSO4, Cu(acac)2, CuPF6(CH3CN)2, CuO, Cu(NO3)2, and mixturesthereof, preferably from the group consisting of PdO, Cu(OAc)2, Cu(OTf)2, CuSO4,Cu(acac)2, CuPF6(CH3CN)2, CuO, Cu(NO3)2, and mixtures thereof. Most preferably, thesubstrate compound is reacted with the chlorine donor in the presence of Cu(NO3)2.These catalysts improve the yield of aryl chlorides significantly compared to theexamples without catalyst or employing other catalysts.The copper salts reported herein encompass the water-free form as well as the knownhydrates of these salts.The catalyst is advantageously present in the method according to the invention in anamount of 1 to 50 mol%, more preferably 5 to 40 mol%, even more preferably 10 to30 mol%, most preferably 15 to 25 mol%, based on the amount of substratecompound. The use of less than 1 mol% catalyst may result in incomplete conversionand low reaction rates, while the use of excess amounts of catalyst higher than 50mol% is costly and thus disadvantageous from an economic perspective.HT / so 230017WO26 April 2024According to a preferred embodiment of the method according to the invention, thecatalyst is used in combination with a second catalyst, preferably a second metalcatalyst. The second catalyst can be a heterogeneous or homogeneous catalyst,preferably a heterogeneous catalyst. The second catalyst is preferably a second metalcatalyst selected from the group consisting of a palladium catalyst, a platinum catalyst,an iron catalyst, a nickel catalyst such as NiO, and mixtures thereof. More preferably,the second catalyst is a palladium catalyst. Even more preferably, the second catalystis PdO, 10%Pd / C, Pd(OH)2 / C, Pd(OAC)2, Pd(TFA)2, Pd(dba)2, Pd(acac)2,Pd(NO3)2·2H2O, and / or PdSO4. Most preferably, the second catalyst is PdO. The use ofPdO as second catalyst improves the yield of aryl chlorides compared to without asecond catalyst or with different second catalysts.If a second catalyst is used, it is advantageously present in an amount of 0.01 to 50mol%, more preferably 0.1 to 30 mol%, even more preferably 1 to 15 mol%, mostpreferably 2.5 to 7.5 mol% based on the amount of substrate compound. The use ofless than 0.01 mol% of the second catalyst may result in incomplete conversion, whilethe use of excess amounts of the second catalyst higher than 50 mol% is costly andthus disadvantageous from an economic perspective.In the method according to the invention, the substrate compound is reacted with thechlorine donor in the presence of an oxidising agent. In a preferred embodiment, theoxidising agent is selected from the group consisting of oxygen, air, nitrate, ozone,hydrogen peroxide, inorganic peroxides, chlorine, nitric acid, permanganate,dichromate, chlorate, sulfuric acid, osmium tetroxide, sodium perborate, nitrogenoxide gases, sodium bismuthate, ceric ammonium nitrate, ceric sulfate, lead dioxide,and mixtures thereof. While other oxidising agents may be suitable as well, the onesmentioned here have the advantage of being readily available on an industrial scale.In a preferred embodiment, the oxidising agent is a combination of a gaseous and anon-gaseous oxidising agent. For example, oxygen or air can be used in combinationHT / so 230017WO26 April 2024with hydrogen peroxide, permanganate or a nitrate salt. According to a preferredembodiment, the oxidising agent is a combination of oxygen and a nitrate salt, mostpreferably a combination of oxygen and sodium nitrate. In this way, a high yields ofthe aryl chloride products may be obtained.In a preferred embodiment of the method according to the invention, a gaseousoxidising agent is employed, preferably oxygen.The non-gaseous oxidising agent, preferably sodium nitrate, is advantageouslyemployed in an amount of 1 to 100 mol%, preferably 5 to 80 mol%, more preferably10 to 50 mol%, most preferably 20 mol% based on the amount of substratecompound. The use of lower amounts of the non-gaseous oxidising agent may result inincomplete conversion, while the use of excess amounts of non-gaseous oxidisingagent higher than 100 mol% is costly and thus disadvantageous from an economicperspective.The gaseous oxidising agent, preferably oxygen, is advantageously employed at apressure of 1 to 100 bar, preferably at 1 to 50 bar, more preferably at 1 to 10 bar,most preferably at 3 bar. Lower pressures may result in incomplete conversion, whilepressures exceeding 100 bar necessitate special equipment and are unsuitable froman industrial perspective.In the method according to the invention, the substrate compound is reacted in thepresence of a solvent. According to a preferred embodiment, the solvent is a proton-containing non-aromatic solvent, preferably a dipolar aprotic solvent, preferablydimethyl sulfoxide. The solvent preferably contains water in an amount of 0.001 to 1wt.%, more preferably 0.05 to 1 wt.%, most preferably 0.05 to 0.1 wt.% based on theamount of solvent.In the method according to the invention, the substrate compound contains an arenemoiety with 3 to 20 carbon atoms. The substrate compound may contain more thanHT / so 230017WO26 April 2024one arene moiety. According to an embodiment, the substrate compound contains twoarene moieties.The substrate compound may contain one or more heteroatoms. According to anembodiment, the substrate compound contains 1 to 20 heteroatoms, preferably 1 to10 heteroatoms. Heteroatoms may be incorporated into the aromatic moiety, inparticular the arene moiety, or into another part of the substrate compound.In an embodiment, the aromatic moiety, in particular the arene moiety of thesubstrate compound contains 1 to 8, preferably 1 to 3, heteroatoms selected from thegroup containing nitrogen, oxygen, sulfur, and phosphorus, preferably nitrogen.The chlorination preferably takes place on the aromatic moiety, in particular the arenemoiety. If the substrate compound contains more than one aromatic moiety, inparticular arene moiety, chlorination may take place on each aromatic moiety, inparticular arene moiety. If the substrate compound contains more than one aromaticmoiety, in particular arene moiety, and one of the aromatic moieties, in particular thearene moieties, contains at least one heteroatom, in particular a nitrogen atom,chlorination preferably takes place on the aromatic moiety, in particular the arenemoiety, that does not contain a heteroatom, in particular a nitrogen atom.In a further embodiment, the aromatic moiety, in particular the arene moiety, of thesubstrate compound contains additional functional groups containing heteroatoms, inparticular amide groups. The additional functional groups containing heteroatoms onthe substrate compound may aid in directing the site at which chlorination takesplace.The method according to the invention can be conducted at various temperatures.Advantageously, the substrate compound is reacted with the chlorine donor at atemperature from 10 to 200 °C, preferably from 100 to 180 °C, more preferably fromHT / so 230017WO26 April 2024130 to 150 °C. At these temperatures, the reaction proceeds sufficiently fast while thecompounds are not degraded.In a preferred embodiment of the method according to the invention, no use ofelectrodes and / or current is required for the reaction to proceed.In a preferred embodiment of the method of the invention, the catalyst contains ametal selected from the group consisting of copper, nickel, cobalt, palladium, andmixtures thereof, and the catalyst is used in combination with a second metal catalystselected from the group consisting of a palladium catalyst, a platinum catalyst, an ironcatalyst, a nickel catalyst, and mixtures thereof. The oxidising agent preferablycomprises a gas. The oxidising agent is more preferably a combination of a gaseousand a non-gaseous oxidising agent. Chlorination preferably chlorination takes place onthe aromatic moiety, in particular the arene moiety. The chlorine donor is preferablyan organic chlorine donor.The invention also relates to the use of a chlorine-containing compound, in particulara solid or liquid organic compound, as chlorine-donor for the chlorination of asubstrate compound containing an aromatic moiety, in particular an arene moiety,with 3 to 20 carbon atoms.According to an embodiment, the invention relates to the use of a chlorine-containingsolid or liquid organic compound as chlorine-donor for the chlorination of a substratecompound containing an aromatic moiety, in particular an arene moiety, with 3 to 20carbon atoms.According to an embodiment of the use according to the invention, the chlorine-containing compound, in particular the chlorine-containing solid or liquid organiccompound, is a chlorinated organic waste compound. Preferably, the chlorine-containing compound, in particular the chlorine-containing solid or liquid organiccompound is selected from solid polymer waste such as post-consumer waste plasticHT / so 230017WO26 April 2024and rubber, liquid laboratory waste such as chlorinated solvents, and mixturesthereof.According to an embodiment of the use according to the invention, the chlorination isconducted in the presence of a catalyst, an oxidising agent, and a solvent. Preferably,the details regarding the catalyst, the oxidising agent, and the solvent as described forthe method according to the invention also apply to the use according to the invention.In the following, the invention is further described by way of examples that are in noway meant to be limiting.EXAMPLESMaterialsInorganic salts including Cu salts, Pd salts and nitrates, solvents, alkyl chlorides andsubstrate compounds containing an arene moiety (if not specified) were purchasedfrom Sigma-Aldrich and used directly unless specified otherwise. Benzoyl chloride,thionyl chloride, 2,4,6-trichlorophenol, N-chlorosuccinimide, chloramine-T, tetrabutylammonium chloride and hydrogen chloride were purchased from Sigma-Aldrich andused directly unless specified otherwise. 1-Chloropiperidine was purchased from AlfaChemistry and used directly. Pure polymers including polyvinylidene chloride (PVDC)Mw≈50’000 / 10’000 / 250’000, polychloroprene (chloroprene rubber, CR),polyepichlorohydrin (PECH) Mw≈700’000, poly(epichlorohydrin-co-ethylene oxide)(PECHEO, epichlorohydrin 64–69 wt.%) Mw≈30’000 and poly(epichlorohydrin-co-CO2) (PECHC) Mw≈20’000 were purchased from Sigma-Aldrich. Compressed air, N2and O2 were purchased from Carbagas. Polyvinylchloride (PVC) or neoprene-basedwater pipe and electrical conduit were obtained from Semadeni AG, electric wire wasobtained from Helukabel, and vacuum tube was obtained from maagtechnic AG. PVDCblisters (Ibuprofen N Zentiva) was purchased from SUN STORE Pharmacies inLausanne. The equivalents of the chlorine-donor were calculated based on the contentof chlorine in the material used, which for the post-consumer waste was determinedHT / so 230017WO26 April 2024 by Schöniger combustion according to the method described in Schöniger, W.,Mikrochim. Acta 1955, 43, 123-129, wherein ion chromatography was used for thedetermination of the chlorine concentration in the absorption solution as described inSection 2.3.2 of Ma, W., Hoffmann, G., Schirmer, M., Chen, G., Rotter, V. S., J. Hazard.Mater.2010, 178, 489-498.General reaction protocol for the chlorination of benzoquinoline as the substratecompound comprising an arene moiety using PVC water pipe as the chlorine-donor 7,8-Benzoquinoline (0.25 mmol), PVC water pipe (1.5 equiv., 0.375 mmol), Cu(NO3)2(20 mol%, 0.05 mmol), PdO (5 mol%, 0.0125 mmol), NaNO3 (20 mol%, 0.05 mmol),biphenyl (0.2 mmol, internal standard) and DMSO (2 mL) were added into a glassinsert vial of an autoclave and charged with O2 (3 bar). The reactor was heated to140 °C for 15 h. After cooling to room temperature, the gas products were collectedwith a Tedlar® gas sampling bag (Sigma-Aldrich) for analysis by gas chromatography.Ethyl acetate (3×3 mL) and an aqueous saturated brine solution (5 mL) were added tothe reaction mixture to extract the organic products. The combined organic phase wasused for analysis. Further purification was achieved using silica gel chromatographywhen required.Analytical MethodsQualitative and quantitative analysis of gas phase products was performed by gaschromatography (GC) using an Agilent 7890B instrument equipped with a hydrogenflame-ionization detector (FID) and a thermal conductivity detector (TCD). The GCyield was determined based on standard gas mixtures and integrated peak areas usingan external standard method. Qualitative and quantitative analysis of crude liquidproducts was performed using an Agilent 7000C GCMS equipped with a hydrogen FID,HT / so 230017WO26 April 2024electron ionization mass detector (EI-MS) and HP-5 nonpolar column. The GC yieldwas determined based on internal standard curves and integrated peak areas.Determination of the molecular weight and polydispersity of the polymers wasperformed using gel permeation chromatography (GPC, Agilent 390-MDS), equippedwith a PL1513-5500 column (Agilent), refractive index detector (RI), and dual-anglelight scattering detector. THF was used as eluent. For the measurement after reaction,to the DMSO solution (2 mL) brine (10 mL) was added and the organic componentsextracted with THF (3×5 mL). The THF extract was used for GPC.1H and 13C NMR spectra were recorded on a Bruker Avance III HD 400 instrumentequipped with a 5 mm BBFO probe. DMSO-d6 or CDCl3 were used as solvent. DMSO-d6was used as the reaction solvent for the reaction that was monitored by 1H NMRspectroscopy. After centrifuging to remove the PdO catalyst, the crude reactionmixture (0.2 mL) was diluted with DMSO-d6 (0.4 mL) and directly used for 1H NMRexperiment.According to the general reaction protocol described above, several syntheses ascompiled in Table 1 were performed using different chlorine donors, and the yields asreported in Table 1 were obtained in these syntheses.Table 1: Syntheses performed using different chlorine donors and respective yieldsExp. No. Chlorine donor Equivalentsa Yieldb1 PVC water pipe 1.5 992 PVC electrical conduit 1.5 80 3PVC electric wire 1.5 964 PVDC raw powder 1.5 995 PVDC blisters 1.5 996 PECH 1.5 997 Neoprene raw chunks 1.5 80HT / so 230017WO26 April 20248 Neoprene vacuum tube 1.5 829 PECHEO 1.5 9910 PECHC 1.5 9911 Dichloromethane 3 8212 Chloroform 3 1213 1,2-Dichloroethane 3 8314 1,1-Dichloroethane 3 9015 1,2,3-Trichloroethane 3 4016 1,2-Dichloroethene 3 8717 Perchloroethene 3 4218 1,6-Dichlorohexane 1.5 9119 2-Chlorohexane 1.5 9520 1,4-Dichlorobutene 1.5 9921 Chlorocyclohexane 3 322 (3-Chlorobutyl)benzene 1.5 9123 Benzyl chloride 1.5 9924 Epichlorohydrin 1.5 9825 Epichlorohydrin carbonate 1.5 98Explanations to Table 1: a – amount of chlorine donor in equivalents, based on theamount of substrate, and calculated based on the content of chlorine; the chlorinecontent of the post-consumer waste was determined by Schöniger combustion asdescribed above; b – yield in % of 10-chlorobenzoquinoline, determined by GC.According to the general reaction protocol described above, several syntheses ascompiled in Table 2 were performed using PVC water pipe as chlorine donor anddifferent substrate compounds as shown in Table 3, and the yields as shown in Table 2of the products shown in Table 4 were obtained in these syntheses.Table 2: Syntheses performed using different substrates and respective yieldsSubstratea Productsb YieldcHT / so 230017WO26 April 2024Exp. Di- Mono- Di- Mono-No. chlorinated chlorinated chlorinated chlorinated26 1a 1b 1b’ 0 9927 2a 2b 2b’ 95 328 3a 3b 3b’ 90 829 4a 4b 4b’ 96 130 5a 5b 5b’ 73 1431 6a 6b 6b’ 74 2232 7a 7b 7b’ 90 433 8a 8b 8b’ 0 9834 9a 9b 9b’ 0 6835 10a 10b 10b’ 2 9536 11a 11b 11b’ 89 1037 12a 12b 12b’ 84 1538 13a 13b 13b’ 11 8539 14a 14b 14b’ 0 9740 15a 15b 15b’ 0 9241 16a 16b 16b’ 45 5242 17a 17b 17b’ 41 5643 18a 18b 18b’ 18 7244 19a 19b 19b’ 9 8145 20a 20b 20b’ 20 7646 21a 21b 21b’ 20 7247 22a 22b 22b’ 16 8148 23a 23b 23b’ 10 7649 24a 24b 24b’ 0 7550 25a 25b 25b’ 0 7851 26a 26b 26b’ 0 6052 27a 27b 27b’ 0 60HT / so 230017WO26 April 2024Explanations to Table 2: a – see Table 3 for structures; b – see Table 4 for structures; c –product yield in % as determined by GC.Table 3: Structures and reference numbers of the substrates listed in Table 2 NN NN Me OMe 1a 2a 3a 4a N N N N CF3Br Me 5a 6a 7a 8a N N N N MeO N 9a 10a 11a 12a N N N N OMe OMe N N N MeO OMe MeO Me N 13a 14a 15a 16a N N N N N N N Ph N 17a 18a 19a 20a OMe N N N N NOMeNCN Me OMe 21a 22a 23a O O N N HNHNF 24a 25a HT / so 230017WO26 April 2024 O O O N S N HNHN26a 27aTable 4: Structures and reference numbers of the products with reported yields aslisted in Table 2Cl Cl Cl N NClNN Me Cl Cl 1b’ 2b 2b’ 3b Cl Cl ClNClNN OMe N CF Me OMe3Cl Cl 3b’ 4b 4b’ 5b Cl Cl ClNClNN Br N CF3Br Cl Me Cl 5b’ 6b 6b’ 7b Cl Cl Cl Cl N N N N Me MeO Cl 7b’ 8b’ 9b’ 10b Cl Cl Cl ClNN N N N Cl Cl 10b’ 11b 11b’ 12b HT / so 230017WO26 April 2024 Cl Cl Cl Cl N N N N OMe OMe N N N N Cl OMe OMe MeO 12b’ 13b 13b’ 14b’ Cl Cl Cl Cl N N N N OMe MeO N N MeO N MeClNCl 15b’ 16b 16b’ 17b Cl Cl Cl N Cl N N N N N N N Cl Cl 17b’ 18b 18b’ 19b Cl Cl Cl N Cl N N N Ph N N N N Ph Cl Cl Me 19b’ 20b 20b’ 21b Cl Cl OMe Cl OMe Cl N N N N N N OMe N OMe N CN Me Cl OMe OMe Cl 21b’ 22b 22b’ 23b Cl O O N N N N CNHNHNCl F Cl 23b’ 24b’ 25b’ O O O N S N HNHNCl Cl 26b’ 27b’ The1H and13C NMR peaks of the products are listed below. HT / so 230017WO26 April 202410-chlorobenzoquinoline (1b’):1H NMR (400 MHz, DMSO) δ=9.07 (dd, J=4.3, 1.9 Hz, 1H), 8.46 (dd, J=8.0, 1.9 Hz, 1H),8.07 (dd, J=7.9, 1.4 Hz, 1H), 8.01 (d, J=8.8 Hz, 1H), 7.95 (d, J=8.8 Hz, 1H), 7.87 (dd,J=7.7, 1.3 Hz, 1H), 7.77–7.66 ppm (m, 2H).13C NMR (101 MHz, DMSO) δ=148.31,145.85, 136.59, 136.53, 131.83, 131.51, 128.64, 128.50, 127.76, 127.48, 126.97,122.76 ppm.2-(2,6-dichlorophenyl)pyridine (2b):1H NMR (400 MHz, DMSO) δ=8.73 – 8.68 (m, 1H), 7.94 (t, J = 7.7 Hz, 1H), 7.59 (d, J =8.1 Hz, 2H), 7.46 (dt, J = 17.0, 8.3 Hz, 3H). 13C NMR (101 MHz, DMSO) δ=155.29,149.96, 138.66, 137.32, 134.07, 131.23, 128.82, 125.31, 123.86.2-(2,6-dichloro-4-methylphenyl)pyridine (3b):1H NMR (400 MHz, DMSO) δ=8.70 (m, J=4.9, 1.8, 1.0 Hz, 1H), 7.91 (td, J=7.7, 1.8 Hz,1H), 7.47–7.34 (m, 4H), 2.35 ppm (d, J=0.9 Hz, 3H).13C NMR (101 MHz, DMSO) δ155.35, 149.91, 141.48, 137.15, 135.81, 133.65, 129.13, 125.45, 123.67, 20.65 ppm.2-(2,6-dichloro-4-methoxyphenyl)pyridine (4b):1H NMR (400 MHz, DMSO) δ=8.68 (dt, J=4.8, 1.4 Hz, 1H), 7.91 (td, J=7.7, 1.9 Hz, 1H),7.47–7.35 (m, 2H), 7.19 (s, 2H), 3.85 ppm (s, 3H).13C NMR (101 MHz, DMSO)δ=160.08, 155.22, 149.89, 137.19, 134.56, 131.19, 125.84, 123.65, 114.63, 56.62 ppm.2-(2,6-dichloro-4-(trifluoromethyll)phenyl)pyridine (5b):1H NMR (400 MHz, DMSO) δ=8.74 (m, J=4.8, 1.8, 1.1 Hz, 1H), 8.03 (d, J=0.8 Hz, 2H),7.98 (td, J=7.7, 1.8 Hz, 1H), 7.49 ppm (m, J=7.7, 5.6, 1.1 Hz, 2H).13C NMR (101 MHz,DMSO) δ=154.24, 150.17, 142.50, 137.53, 135.34, 132.08, 131.74, 131.41, 131.08,127.06, 125.82, 125.78, 125.75, 125.71, 125.03, 124.34, 124.27, 121.63, 118.91 ppm.2-(2,6-dichloro-4-bromophenyl)pyridine (6b): HT / so 230017WO26 April 20241H NMR (400 MHz, DMSO) δ=8.71 (m, J=4.9, 1.9, 1.0 Hz, 1H), 7.95 (td, J=7.7, 1.8 Hz,1H), 7.91 (s, 2H), 7.51–7.40 ppm (m, 2H).13C NMR (101 MHz, DMSO) δ=154.48,150.10, 138.03, 137.45, 135.09, 131.27, 125.32, 124.09, 122.46 ppm.2-(2,6-dichloro-phenyl)-3-methyl-pyridine (7b):1H NMR (400 MHz, DMSO) δ=8.52 (m, J=4.8, 1.6, 0.7 Hz, 1H), 7.80 (m, J=7.7, 1.7, 0.9 Hz,1H), 7.62 (dd, J=8.0, 0.8 Hz, 2H), 7.50 (dd, J=8.8, 7.3 Hz, 1H), 7.39 (dd, J=7.8, 4.8 Hz,1H), 2.03 ppm (s, 3H). 13C NMR (101 MHz, DMSO) δ=154.91, 147.55, 138.41, 137.99,133.91, 132.09, 131.24, 128.81, 124.12, 18.05 ppm.2-(2-chloronaphthalen-1-yl)pyridine (8b’):1H NMR (400 MHz, CDCl3) δ=8.76 (m, J=4.9, 1.8, 1.0 Hz, 2H), 7.79 (m, J=8.5, 6.9, 4.9 Hz,6H), 7.48 (d, J=8.8 Hz, 2H), 7.45–7.24 ppm (m, 10H).13C NMR (101 MHz, CDCl3)δ=156.66, 149.83, 136.41, 136.10, 133.24, 132.12, 130.70, 129.76, 128.04, 127.18,126.01, 125.69, 122.67 ppm,2-(2-chloro-6-methoxyphenyl)pyridine (9b’):1H NMR (400 MHz, CDCl3) δ=8.65 (m, J=4.9, 1.8, 1.0 Hz, 1H), 7.67 (td, J=7.7, 1.8 Hz,1H), 7.27–7.16 (m, 3H), 7.01 (dd, J=8.1, 1.0 Hz, 1H), 6.81 (dd, J=8.4, 1.0 Hz, 1H), 3.64ppm (s, 3H). 13C NMR (101 MHz, CDCl3) δ=158.25, 154.97, 149.47, 136.05, 134.13,129.79, 129.20, 125.67, 122.36, 121.82, 109.53, 77.31, 56.11 ppm.3-(2-chlorophenyl)isoquinoline (10b’):1H NMR (400 MHz, CDCl3) δ=8.19–8.07 (m, 2H), 7.81 (dd, J=8.0, 1.5 Hz, 1H), 7.72–7.64(m, 2H), 7.66–7.58 (m, 1H), 7.51 (m, J=8.2, 6.9, 1.2 Hz, 1H), 7.44 (dd, J=7.2, 2.0 Hz, 1H),7.33 ppm (pd, J=7.4, 1.8 Hz, 2H).13C NMR (101 MHz, CDCl3) δ=157.45, 148.11, 139.70,135.67, 132.39, 131.71, 130.11, 129.89, 129.72, 129.69, 127.57, 127.19, 127.15,126.79, 122.79, 77.23 ppm.1-(2,6-dichlorophenyl)isoquinoline (11b): HT / so 230017WO26 April 20241H NMR (400 MHz, CDCl3) δ=8.61 (d, J=5.7 Hz, 1H), 7.86 (dt, J=8.3, 1.1 Hz, 1H), 7.72–7.59 (m, 2H), 7.51–7.38 (m, 4H), 7.32 ppm (dd, J=8.9, 7.2 Hz, 1H). 13C NMR (101 MHz,CDCl3) δ=156.70, 142.49, 136.96, 136.36, 135.20, 130.45, 130.24, 128.18, 127.80,127.16, 126.04, 121.01, 77.23 ppm.2-(2,6-dichlorophenyl)pyrimidine (12b):1H NMR (400 MHz, DMSO) δ=9.01 (d, J=5.0 Hz, 2H), 7.66–7.59 (m, 3H), 7.54 ppm (dd,J=9.0, 7.1 Hz, 1H). 13C NMR (101 MHz, DMSO) δ=163.64, 158.35, 137.82, 133.32,131.65, 128.78, 121.38 ppm.2-(2-chloro-4,5-dimethoxyphenyl)pyrimidine (13b’):1H NMR (400 MHz, CDCl3) δ=8.89 (d, J=4.9 Hz, 2H), 7.39 (s, 1H), 7.28 (t, J=4.9 Hz, 1H),7.01 (s, 1H), 3.96 ppm (d, J=1.8 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ=165.34, 157.23,157.01, 150.39, 147.83, 129.50, 124.69, 118.95, 114.06, 113.52, 77.23, 56.28, 56.18ppm.2-(2-chloro-6-methoxyphenyl)pyrimidine (14b’):1H NMR (400 MHz, CDCl3) δ=8.83 (d, J=4.9 Hz, 2H), 7.30–7.17 (m, 2H), 7.02 (dd, J=8.1,0.9 Hz, 1H), 6.84 (dd, J=8.4, 0.9 Hz, 1H), 3.68 ppm (s, 3H).13C NMR (101 MHz, CDCl3)δ=164.23, 158.11, 157.31, 133.54, 130.30, 128.29, 121.77, 119.55, 109.60, 77.23,56.16 ppm.2-(2-chloro-4-methoxy-6-methylphenyl)pyrimidine (15b’):1H NMR (400 MHz, CDCl3) δ=8.80 (d, J=4.9 Hz, 2H), 7.21 (t, J=4.9 Hz, 1H), 6.79 (d, J=2.5Hz, 1H), 6.66 (dd, J=2.4, 0.9 Hz, 1H), 3.74 (s, 3H), 2.03 ppm (s, 3H). 13C NMR (101 MHz,CDCl3) δ=166.22, 159.75, 157.24, 139.05, 133.27, 131.14, 119.27, 114.77, 112.23,55.52, 20.34 ppm.2-(2,6-dichlorophenyl)-5-methoxypyrimidine (16b): HT / so 230017WO26 April 20241H NMR (500 MHz, CDCl3) δ=8.58 (s, 2H), 7.42 (d, J=8.0 Hz, 2H), 7.30 (dd, J=14.8, 6.5Hz, 1H), 4.02 ppm (s, 3H). 13C NMR (126 MHz, CDCl3) δ=156.51, 152.19, 143.52,137.29, 134.49, 130.12, 128.08, 56.03 ppm.2-(2-chlorophenyl)-5-methoxypyrimidine (16b’):1H NMR (500 MHz, CDCl3) δ=8.56 (s, 3H), 7.72 (dd, J=6.1, 3.4 Hz, 2H), 7.55–7.48 (m,2H), 7.45–7.28 (m, 4H), 4.01 ppm (s, 5H).13C NMR (126 MHz, CDCl3) δ=158.22, 151.90,143.53, 143.20, 137.44, 132.63, 131.55, 130.51, 130.03, 128.08, 126.79, 56.03 ppm.2-(2,6-dichlorophenyl)quinazoline (17b):1H NMR (500 MHz, CDCl3) δ=9.59 (s, 1H), 8.18 (d, J=8.5 Hz, 1H), 8.09–7.99 (m, 2H),7.78 (m, J=8.1, 6.9, 1.1 Hz, 1H), 7.47 (d, J=8.1 Hz, 2H), 7.36 ppm (dd, J=8.7, 7.5 Hz, 1H).13C NMR (126 MHz, CDCl3) δ=160.86, 160.38, 150.35, 137.90, 134.64, 134.26, 130.25,128.71, 128.53, 128.19, 127.30, 123.61 ppm.2-(2-chlorophenyl)quinazoline (17b’):1H NMR (500 MHz, CDCl3) δ=9.58 (d, J=16.0 Hz, 1H), 8.16 (d, J=8.2 Hz, 1H), 8.09–7.96(m, 3H), 7.89–7.82 (m, 1H), 7.82–7.70 (m, 1H), 7.60–7.53 (m, 1H), 7.50–7.33 ppm (m,3H).13C NMR (126 MHz, CDCl3) δ=162.02, 160.29, 150.38, 138.30, 134.64, 134.44,132.92, 131.81, 130.58, 130.36, 130.25, 128.71, 128.68, 128.54, 128.19, 128.11,127.31, 127.19, 126.93, 123.31 ppm.1-(2-chlorophenyl)-1H-pyrazole (18b’):1H NMR (400 MHz, CDCl3) δ=7.81 (d, J=2.4 Hz, 3H), 7.68 (d, J=1.9 Hz, 3H), 7.56–7.47(m, 3H), 7.47–7.35 (m, 3H), 7.35–7.21 (m, 6H), 6.47–6.37 ppm (m, 3H).13C NMR (101MHz, CDCl3) δ=140.93, 131.30, 130.66, 130.63, 129.00, 128.68, 128.37, 127.82,127.67, 106.69, 106.66 ppm.2-(2-chlorophenyl)-2H-indazole (19b’):1H NMR (400 MHz, CDCl3) δ=8.27 (d, J=1.0 Hz, 1H), 7.76–7.58 (m, 3H), 7.57–7.46 (m,1H), 7.44–7.24 (m, 3H), 7.07 ppm (m, J=8.5, 6.6, 0.9 Hz, 1H).13C NMR (101 MHz, CDCl3)HT / so 230017WO26 April 2024δ=149.43, 138.64, 130.70, 129.97, 129.00, 128.59, 127.71, 126.95, 125.23, 122.45,122.02, 120.53, 117.95, 77.23 ppm.1-(3-chloro-[1,1'-biphenyl]-4-yl)-1H-pyrazole (20b’):1H NMR (400 MHz, CDCl3) δ=7.86 (dd, J=2.4, 0.6 Hz, 1H), 7.69 (dd, J=11.4, 1.9 Hz, 2H),7.63–7.48 (m, 4H), 7.46–7.29 (m, 3H), 6.43 ppm (dd, J=2.5, 1.9 Hz, 1H).13C NMR (101MHz, CDCl3) δ=142.22, 141.01, 138.79, 137.13, 131.32, 129.11, 129.06, 128.40,128.27, 127.92, 127.12, 126.30, 106.75, 77.23 ppm.1-(2-chloro-5-methylphenyl)-1H-pyrazole (21b’):1H NMR (400 MHz, CDCl3) δ=7.90 (d, J=2.5 Hz, 1H), 7.76 (d, J=1.8 Hz, 1H), 7.46–7.38(m, 2H), 7.16 (dd, J=8.4, 2.2 Hz, 1H), 6.49 (t, J=2.2 Hz, 1H), 2.40 ppm (s, 3H). 13C NMR(101 MHz, CDCl3) δ=140.79, 138.01, 137.79, 131.29, 130.27, 129.72, 128.26, 124.97,106.55, 77.23, 20.77 ppm.1-(2-chloro-3,4,5-trimethoxyphenyl)-1H-pyrazole (22b’):1H NMR (400 MHz, CDCl3) δ=7.89 (dd, J=2.5, 0.7 Hz, 1H), 7.73 (dd, J=1.7, 0.6 Hz, 1H),6.93 (s, 2H), 6.48 (dd, J=2.5, 1.8 Hz, 1H), 3.95 (s, 7H), 3.89 ppm (s, 3H). 13C NMR (101MHz, CDCl3) δ=153.77, 140.93, 136.71, 136.40, 127.02, 107.54, 97.29, 77.24, 61.05,56.34 ppm.3-chloro-4-(1H-pyrazol-1-yl)benzonitrile (23b’):1H NMR (400 MHz, CDCl3) δ=8.01 (dd, J=2.6, 0.6 Hz, 1H), 7.80–7.70 (m, 3H), 7.61 (dd,J=8.4, 1.8 Hz, 1H), 6.47 ppm (dd, J=2.6, 1.8 Hz, 1H).13C NMR (101 MHz, CDCl3)δ=142.15, 141.55, 134.60, 131.41, 131.24, 127.86, 127.55, 116.90, 112.18, 107.93,77.23 ppm.2-chloro-N-(quinolin-8-yl)benzamide (24b’):1H NMR (400 MHz, CDCl3) δ=10.61 (s, 1H), 8.85–8.78 (m, 2H), 8.52 (dd, J=8.6, 1.7 Hz,1H), 8.04–7.96 (m, 2H), 7.58 (d, J=8.4 Hz, 1H), 7.56–7.43 ppm (m, 4H). 13C NMR (101HT / so 230017WO26 April 2024MHz, CDCl3) δ=165.44, 148.79, 139.34, 134.91, 133.90, 133.50, 132.03, 128.87,127.34, 127.30, 126.04, 124.51, 122.44, 116.49, 77.24 ppm.2-chloro-4-fluoro-N-(quinolin-8-yl)benzamide (25b’):1H NMR (500 MHz, CDCl3) δ=10.38 (s, 1H), 9.31 (dt, J=8.9, 1.5 Hz, 1H), 9.07–9.01 (m,1H), 8.98–8.89 (m, 1H), 8.64 (dd, J=8.8, 1.6 Hz, 1H), 8.61 (s, 0H), 7.80–7.74 (m, 1H),7.30–7.17 ppm (m, 4H).13C NMR (126 MHz, CDCl3) δ=163.43, 162.44, 149.29, 139.81,139.59, 137.60, 133.64, 133.41, 127.51, 124.83, 121.75, 116.49, 116.29, 114.51, 77.25ppm.3-chloro-N-(quinolin-8-yl)furan-2-carboxamide (26b’):1H NMR (500 MHz, CDCl3) δ=10.75 (s, 1H), 8.95 (dd, J=4.1, 1.6 Hz, 1H), 8.84 (d, J=8.3Hz, 1H), 8.61 (dd, J=8.6, 1.8 Hz, 1H), 7.69–7.63 (m, 2H), 7.62 (dd, J=8.5, 4.2 Hz, 1H),7.33 (d, J=3.5 Hz, 1H), 6.62 ppm (dd, J=3.5, 1.7 Hz, 1H). 13C NMR (126 MHz, CDCl3)δ=156.35, 148.91, 148.17, 144.66, 139.21, 133.50, 133.43, 127.28, 126.04, 124.65,122.47, 116.57, 115.40, 112.55 ppm.3-chloro-N-(quinolin-8-yl)thiophene-2-carboxamide (27b’):1H NMR (400 MHz, CDCl3) δ=11.29 (s, 1H), 8.85 (dd, J=4.2, 1.6 Hz, 1H), 8.77 (d, J=8.4Hz, 1H), 8.53 (dd, J=8.6, 1.6 Hz, 1H), 7.61–7.46 (m, 3H), 7.02 ppm (d, J=5.2 Hz, 1H). 13CNMR (101 MHz, CDCl3) δ=158.69, 149.02, 139.47, 133.96, 133.82, 133.37, 130.20,129.86, 127.27, 126.04, 125.02, 124.24, 122.46, 117.25, 77.23 ppm.Further experiments were performed according to the general reaction protocoldescribed above with varying reaction conditions using 7,8-benzoquinoline assubstrate and PVC water pipe as chlorine donor as compiled in Table 5.Table 5: Syntheses performed with varying reaction conditionsExp. Catalysta Second NaNO3c GaseousTemp.dYieldeNo. catalystb oxidisingagentHT / so 230017WO26 April 2024CuO, 20 mol% PdO, 5 mol% 20 O2, 3 bar 140 58CuSO4, 20 PdO, 5 mol% 20 O2, 3 bar 140 38mol%Cu(OAc)2, 20 PdO, 5 mol% 20 O2, 3 bar 140 28mol%Cu(NO3)2, 20 PdO, 5 mol% 20 O2, 3 bar 140 99mol%Cu(OTf)2, 20 PdO, 5 mol% 20 O2, 3 bar 140 37mol%Cu(acac)2, 20 PdO, 5 mol% 20 O2, 3 bar 140 36mol%CuPF6(CH3CN)2, PdO, 5 mol% 20 O2, 3 bar 140 3720 mol%PdO, 10 mol% – 100 O2, 3 bar 140 7Cu(NO3)2, 5 PdO, 10 mol% 100 O2, 3 bar 140 28mol%Cu(NO3)2, 10 PdO, 10 mol% 100 O2, 3 bar 140 41mol%Cu(NO3)2, 20 PdO, 10 mol% 100 O2, 3 bar 140 73mol%Cu(NO3)2, 30 PdO, 10 mol% 100 O2, 3 bar 140 73mol%Cu(NO3)2, 20 – 100 O2, 3 bar 140 29mol%Cu(NO3)2, 20 10% Pd / C, 10 100 O2, 3 bar 140 74mol% mol%Cu(NO3)2, 20 Pd(OH)2 / C, 10 100 O2, 3 bar 140 75mol% mol%Cu(NO3)2, 20 Pd(OAc)2, 10 100 O2, 3 bar 140 34mol% mol%HT / so 230017WO26 April 2024Cu(NO3)2, 20 Pd(TFA)2, 10 100 O2, 3 bar 140 39mol% mol%Cu(NO3)2, 20 Pd(dba)2, 10 100 O2, 3 bar 140 25mol% mol%Cu(NO3)2, 20 Pd(acac)2, 10 100 O2, 3 bar 140 52mol% mol%Cu(NO3)2, 20 Pd(NO3)2·2H2O, 100 O2, 3 bar 140 39mol% 10 mol%Cu(NO3)2, 20 PdSO4, 10 100 O2, 3 bar 140 24mol% mol%Cu(NO3)2, 20 NiO, 10 mol% 100 O2, 3 bar 140 26mol%Cu(NO3)2, 20 PdO, 2.5 mol% 100 O2, 3 bar 140 69mol%Cu(NO3)2, 20 PdO, 5 mol% 0 O2, 3 bar 140 52mol%Cu(NO3)2, 20 PdO, 5 mol% 10 O2, 3 bar 140 87mol%Cu(NO3)2, 20 PdO, 5 mol% 40 O2, 3 bar 140 98mol%Cu(NO3)2, 20 PdO, 5 mol% 60 O2, 3 bar 140 93mol%Cu(NO3)2, 20 PdO, 5 mol% 100 O2, 3 bar 140 84mol%Cu(NO3)2, 20 PdO, 5 mol% 160 O2, 3 bar 140 82mol%Cu(NO3)2, 20 PdO, 5 mol% 240 O2, 3 bar 140 74mol%Cu(NO3)2, 20 PdO, 5 mol% 20 O2, 3 bar 120 5mol%HT / so 230017WO26 April 202484 Cu(NO3)2, 20 PdO, 5 mol% 20 O2, 3 bar 130 37mol%85 Cu(NO3)2, 20 PdO, 5 mol% 20 O2, 3 bar 150 99mol%86 Cu(NO3)2, 20 PdO, 5 mol% 20 O2, 1 bar 140 80mol%87 Cu(NO3)2, 20 PdO, 5 mol% 20 O2, 5 bar 140 99mol%88 Cu(NO3)2, 20 PdO, 5 mol% 20 Air, 1 bar 140 3mol%89 Cu(NO3)2, 20 PdO, 5 mol% 20 Air, 10 140 38mol% bar90f Cu(NO3)2, 20 PdO, 5 mol% 20 N2, 1 bar 140 0mol%Explanations to Table 5: a –amount of catalyst in mol% based on 7,8-benzoquinoline; b– amount of second catalyst in mol% based on 7,8-benzoquinoline; c – amount ofNaNO3 in mol% based on 7,8-benzoquinoline;d– reaction temperature in °C;e– yieldin % of 10-chlorobenzoquinoline, determined by GC, f – comparative example.According to the general reaction protocol for the chlorination of benzoquinoline asthe substrate compound described above, further syntheses as compiled in Table 6were performed using further different chlorine donors, and the yields as reported inTable 6 were obtained in these syntheses.Table 6: Syntheses performed using different chlorine donors and respective yieldsExp. No. Chlorine donor Equivalentsa Yieldb91 Benzoyl chloride 1.5 7492 Thionyl chloride 1.5 9893 2,4,6-trichlorophenol 1.5 9194 1-chloropiperidine 1.5 93HT / so 230017WO26 April 202495 N-chlorosuccinimide 1.5 5696 Chloramine-T 1.5 9997 Tetrabutyl ammonium chloride 1.5 3598 Hydrogen chloride 1.5 92Explanations to Table 6: a – amount of chlorine donor in equivalents, based on theamount of substrate, and calculated based on the content of chlorine; b – yield in % of10-chlorobenzoquinoline, determined by GC.As elucidated in the given examples, the chlorination of substrate compoundscontaining an aromatic moiety, in particular an arene moiety, proceeds in thepresence of a chlorine-donor, a catalyst, an oxidising agent, and a solvent. Good yieldscan be obtained for different catalysts and catalyst combinations. The method allowsfor a great flexibility concerning the oxidising agent. Moreover, waste productscontaining chlorinated hydrocarbon compounds can be used directly as chlorine-donor in the method according to the invention.HT / so 230017WO26 April 2024

Claims

April 26, 2024C l a i m s1. Method for chlorination of a substrate compound containing an aromatic moiety,in particular an arene moiety, with 3 to 20 carbon atoms, wherein the substratecompound is reacted with a chlorine-donor, in particular an organic chlorinedonor, in the presence of a catalyst, an oxidising agent, and a solvent.

2. Method according to claim 1, wherein the chlorine-donor contains a chlorinatedhydrocarbon compound.

3. Method according to claims 1 and 2, wherein the chlorine-donor, in particular thechlorinated hydrocarbon compound, can be solid or liquid at 25°C, preferablywherein the chlorinated hydrocarbon compound contains a chlorine atomconnected to an aliphatic moiety.

4. Method according to any of the preceding claims, wherein the chlorine-donorcontains a chlorine atom connected to a carbon atom, a nitrogen atom, a sulfuratom, or a hydrogen atom, in particular connected to a nitrogen atom, a sulfuratom, or a hydrogen atom, and / or wherein the chlorine-donor is selected fromthe group consisting of polyvinyl chloride, polyvinylidene chloride,polyepichlorohydrin, neoprene, poly(epichlorohydrin-co-ethylene oxide),poly(epichlorohydrin-co-CO2), dichloromethane, chloroform, 1,2-dichloroethane,1,1-dichloroethane, 1,1,2-trichloroethane, 1,2-dichloroethene, perchloroethene,1,6-dichlorohexane, 2-chlorohexane, 1,4-dichlorobutene, chlorocyclohexane, (3-chlorobutyl)benzene, benzyl chloride, epichlorohydrin, epichlorohydrincarbonate, benzoyl chloride, thionyl chloride, 2,4,6-trichlorophenol, 1-chloropiperidine, N-chlorosuccinimide, chloramine-T, tetrabutylammoniumchloride, HCl, and mixtures thereof, preferably selected from the group consisting- 2 - of polyvinyl chloride, polyvinylidene chloride, polyepichlorohydrin, neoprene,poly(epichlorohydrin-co-ethylene oxide), poly(epichlorohydrin-co-CO2),dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloroethene,1,6-dichlorohexane, 2-chlorohexane, 1,4-dichlorobutene, (3-chlorobutyl)benzene, benzyl chloride, epichlorohydrin, epichlorohydrincarbonate, thionyl chloride, 2,4,6-trichlorophenol, 1-chloropiperidine, HCl, andmixtures thereof.

5. Method according to any of the preceding claims, wherein the catalyst contains ametal, preferably contains a metal selected from the group consisting of copper,nickel, cobalt, palladium, and mixtures thereof, more preferably contains copperand / or palladium, even more preferably contains a palladium compound and / oracopper salt selected from the group consisting of PdO, Cu(OAc)2, Cu(OTf)2,CuSO4, Cu(acac)2, CuPF6(CH3CN)2, CuO, and / or Cu(NO3)2 and mixtures thereof,most preferably contains Cu(NO3)2, and / or wherein the catalyst is aheterogeneous or homogeneous catalyst, preferably a homogeneous catalyst.

6. Method according to any of the preceding claims, wherein the catalyst ispreferably used in combination with a second catalyst, preferably a second metalcatalyst selected from the group consisting of a palladium catalyst, a platinumcatalyst, an iron catalyst, a nickel catalyst such as NiO, and mixtures thereof, morepreferably a palladium catalyst, even more preferably PdO, 10%Pd / C, Pd(OH)2 / C,Pd(OAC)2, Pd(TFA)2, Pd(dba)2, Pd(acac)2, Pd(NO3)2·2H2O, and / or PdSO4 andmixtures thereof, most preferably PdO.

7. Method according to any of the preceding claims, wherein the oxidising agentcontains a compound selected from the group consisting of oxygen, air, nitrate,ozone, hydrogen peroxide, inorganic peroxides, chlorine, nitric acid,permanganate, dichromate, chlorate, sulfuric acid, osmium tetroxide, sodiumperborate, nitrogen oxide gases, sodium bismuthate, ceric ammonium nitrate,ceric sulfate, lead dioxide, and mixtures thereof.HT / so 230017WO26 April 2024- 3 -8. Method according to any of the preceding claims, wherein the oxidising agent is acombination of a gaseous and a non-gaseous oxidising agent, more preferably acombination of oxygen and a nitrate salt, in particular sodium nitrate,and / orwherein the solvent is a proton-containing non-aromatic solvent, preferably adipolar aprotic solvent, preferably dimethyl sulfoxide, and / or wherein thesolvent contains water, preferably contains water in an amount of 0.001 to 1wt.%, more preferably 0.05 to 1 wt.%, most preferably 0.05 to 0.1 wt.% based onthe amount of solvent.

9. Method according to any of the preceding claims, wherein the aromatic moiety, inparticular the arene moiety, of the substrate compound contains 1 to 8,preferably 1 to 3, heteroatoms selected from the group containing nitrogen,oxygen, sulfur, and phosphorus, preferably nitrogen.

10. Method according to any of the preceding claims, wherein the chlorination takesplace on the aromatic moiety, in particular the arene moiety.

11. Method according to any of the preceding claims, wherein the substratecompound is reacted with the chlorine-donor at a temperature from 10 to 200 °C,preferably from 100 to 180 °C, more preferably from 130 to 150 °C, and / orwherein the chlorine-donor is employed in an amount of 1.0 to 5.0 equivalents,more preferably 1.0 to 3.0 equivalents, even more preferably 1.0 to 2.0equivalents, most preferably 1.5 equivalents, based on the amount of substratecompound, and / or wherein the catalyst is employed in an amount of 1 to 50mol% based on the amount of substrate compound, more preferably 5 to 40mol%, even more preferably 10 to 30 mol%, most preferably 15 to 25 mol%.

12. Method according to any of claims 6 to 11, wherein the second catalyst isemployed in an amount of 0.01 to 50 mol% based on the amount of substrateHT / so 230017WO26 April 2024- 4 - compound, more preferably 0.1 to 30 mol%, even more preferably 1 to 15 mol%,most preferably 2.5 to 7.5 mol%.

13. Method according to any of claims 7 to 12, wherein the non-gaseous oxidisingagent is employed in an amount of 1 to 100 mol% based on the amount ofsubstrate compound, preferably 5 to 80 mol%, more preferably 10 to 50 mol%,most preferably 20 mol%, and / or wherein the gaseous oxidising agent isemployed at a pressure of 1 to 100 bar, preferably at 1 to 50 bar, more preferablyat 1 to 10 bar, most preferably at 3 bar.

14. Use of a chlorine-containing compound, in particular a chlorine-containing solidor liquid organic compound, more particularly a chlorinated organic wastecompound, as chlorine-donor for the chlorination of a substrate compoundcontaining an aromatic moiety, in particular an arene moiety, with 3 to 20 carbonatoms.

15. Use according to claim 14, wherein the chlorine-containing compound, inparticular the chlorine-containing solid or liquid organic compound, is selectedfrom solid polymer waste such as post-consumer waste plastic and rubber, liquidlaboratory waste such as chlorinated solvents, and mixtures thereof, and / orwherein the chlorination is conducted in the presence of a catalyst, an oxidisingagent, and a solvent, in particular as detailed in any one of claims 1 to 13.HT / so 230017WO26 April 2024

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