WO2026012766A1 - Process for the dehydrohalogenation of halogenated hydrocarbons - Google Patents
Process for the dehydrohalogenation of halogenated hydrocarbonsInfo
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- WO2026012766A1 WO2026012766A1 PCT/EP2025/068158 EP2025068158W WO2026012766A1 WO 2026012766 A1 WO2026012766 A1 WO 2026012766A1 EP 2025068158 W EP2025068158 W EP 2025068158W WO 2026012766 A1 WO2026012766 A1 WO 2026012766A1
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- Prior art keywords
- sulfoxide
- containing resin
- halogenated hydrocarbon
- groups
- process according
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon, said process comprising contacting at a temperature T1 ranging from 40°C to 200 °C the halogenated hydrocarbon with a sulfoxide containing resin, optionally in the presence of a base; wherein the sulfoxide containing resin comprises a plurality of sulfoxide groups and is free of hydrolysable groups; and wherein halogen atom (X) is selected from F, Cl, Br and I.
Description
PROCESS FOR THE DEHYDROHALOGENATION OF HALOGENATED HYDROCARBONS
Cross-reference to related application
[0001 ] This application claims priority to European application No. 24187597.0 filed on July 10, 2024, the whole content of this application being incorporated herein by reference for all purposes.
Technical Field
[0002] The invention relates to a process for the manufacture of unsaturated hydrocarbons by catalytic dehydrohalogenation of halogenated hydrocarbons in the presence of a sulfoxide containing resin.
Background Art
[0003] The dehydrohalogenation of halogenated hydrocarbons for the preparation of unsaturated compounds is a common synthetic process at industrial level.
[0004] For instance, vinylidene chloride is prepared commercially by the dehydrochlorination of 1 ,1 ,2-trichloroethane using calcium or sodium hydroxide. The process produces vinylidene chloride in very high yields (approximately 90%) but has the drawback that great amounts of inorganic byproducts (e.g. CaCl2 or NaCI) are generated and need to be disposed of or recycled. Catalytic processes producing hydrogen chloride as a by-product would therefore be more advantageous.
[0005] J. Macromol.Sci.-Chem., A12(2), 249-260 (1978) relates to the kinetics of the alkaline dehydrochlorination of polyvinylchloride (PVC) in the presence of alcoholic KOH in THF solution at 9.5°C. Small amounts of DMSO in the solvent are found to increase the reaction rate. Material with poly-ene sequences is obtained.
[0006] US 5210344 discloses a process for the preparation of vinylidene chloride by dehydrochlorination of 1 ,1 ,2-trichloroethane in the presence of a cyclic amine having a pKa greater than 11 . Exemplary cyclic amines with a pKa greater than 11 are 2,2,6,6-tetramethylpiperidine, 1 ,2,2,6, 6-pentamethylpiperidine, 2,2,4- trimethylpiperidine, 1 ,8-diazabicyclo-[5.4.0]-undec-7-ene, and 1 ,5- diazabicyclo-[4.3.0]-non-5-ene.
[0007] US 2016/0176790 discloses a catalytic process for the dehydrochlorination of chlorinated hydrocarbons to produce unsaturated compounds involving guanidinium salts or their guanidine precursors. The inventors have shown that the use of said guanidinium salts, or their guanidine precursors, in the dehydrochlorination reaction of 1 ,1 ,2-trichloroethane is selective in the production of vinylidene chloride.
[0008] There is a need for a process for the dehydrohalogenation of a halogenated hydrocarbon not requiring the use of inorganic bases.
[0009] There is a need for a catalytic process for the dehydrohalogenation of a halogenated hydrocarbon operating at low temperature and using simple experimental or industrial set up.
[0010] There is a need for a catalytic process for the dehydrohalogenation of a halogenated hydrocarbon where catalytic sites can be supported on a polymeric backbone for simplifying operating conditions.
[0011 ] It has now been found that the use of a sulfoxide containing resin, optionally in the presence of a base, provides suitable catalytic processes for the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon.
Summary of invention
[0012] With the aim of fulfilling the above needs, the Applicant faced the problem of providing a new process suitable for the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon in mild operating conditions.
[0013] Thus, in a first aspect, the present application relates to a process for the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon, said process comprising contacting at a temperature T1 ranging from 40°C to 200 °C the halogenated hydrocarbon with a sulfoxide containing resin, optionally in the presence of a
base; wherein the sulfoxide containing resin comprises a plurality of grafted sulfoxide groups and is free of hydrolysable groups; and wherein halogen atom (X) is selected from F, Cl, Br and I, preferably from F and Cl and more preferably is Cl.
[0014] Without being bound to any theory, sulfoxide groups grafted onto the sulfoxide containing resin are considered to act as catalyst for the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon.
[0015] In another aspect the present invention relates to a column packed with at least one sulfoxide containing resin comprising a plurality of grafted sulfoxide groups and being free of hydrolysable groups.
[0016] Still in another aspect the present invention relates to the use of a column packed with a sulfoxide containing resin for conducting the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon.
[0017] Finally, the present application relates to an experimental or an industrial set up comprising a column packed with a sulfoxide containing resin suitable for conducting the process according to the invention, wherein the halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms yields the corresponding unsaturated hydrocarbon.
Detailed description
[0018] The object of the invention is a process for the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon, said process comprising contacting at a temperature T1 ranging from 40°C to 200 °C the halogenated hydrocarbon with a sulfoxide containing resin, optionally in the presence of a base;
wherein the sulfoxide containing resin comprises a plurality of sulfoxide groups and is free of hydrolysable groups; and wherein halogen atom (X) is selected from F, Cl, Br and I, preferably from F and Cl and more preferably is Cl.
[0019] The expression “vicinal carbon atoms” is used herein in its generally recognized meaning to indicate two adjacent carbon atoms. Thus the halogenated hydrocarbon comprises at least one halogen atom (X) bound to a first carbon atom and at least one hydrogen atom bound to a carbon atom adjacent to the first.
[0020] Any halogenated hydrocarbon which possesses at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms may be dehydrohalogenated using the process of the invention.
[0021 ] Typically, the halogenated hydrocarbon is selected from the group of compounds of formula (I): RR1CX-CHR2R3 (I) and the corresponding unsaturated hydrocarbon obtained by the dehydrohalogenation process is a compound of formula (II): RRI C=CR2R3 (II).
[0022] In formulas (I) and (II) each of R, R1, R2 and R3 is independently selected from the group consisting of H, X’, C1-C10 optionally halogenated alkyl. Typically each of R, R1, R2 and R3 is independently selected from the group consisting of H, CX, C1-C5 alkyl. Wherein X’ is selected from F, Cl, Br and I, preferably from F and Cl and more preferably is Cl.
[0023] In an embodiment of the process of the invention R and R2 are simultaneously hydrogen.
[0024] In an advantageous aspect of said embodiment R1 and R3 are selected from the group consisting of H and Cl. Preferably when R1 is H then R3 is Cl and the compound of formula (II) is vinyl chloride.
[0025] In a preferred embodiment of the invention compound of formula (I) is 1 ,1 ,2- trichloroethane, that is RI =R3=H, R=R2=CI and X=CI, and compound of formula (II) is vinylidene chloride.
[0026] In another preferred embodiment of the invention compound of formula (I) is 1 ,2-dichloroethane, that is R=RI=R2=H, R3=CI and X=CI, and compound of formula (II) is vinyl chloride.
[0027] Still in a preferred embodiment of the invention compound of formula (I) is 1- chloro-1 ,1 -difluoroethane, that is R=Ri=F, R2=R3=H and X=CI, and compound of formula (II) is vinylidene fluoride.
[0028] Finally in a preferred embodiment of the invention compound of formula (I) is 1 -bromo-1 ,1 -difluoroethane, that is R=Ri=F, R2=R3=H and X=Br, and compound of formula (II) is vinylidene fluoride.
[0029] In some embodiments, contacting the halogenated hydrocarbon with the sulfoxide containing resin is carried out by passing the halogenated hydrocarbon, optionally in the presence of a base, through a least one column packed with the sulfoxide containing resin and thermostated at the temperature T1 ranging from 40°C to 200°C.
[0030] Generally the column is thermostated at a temperature T1 ranging from 40°C to 200°C; often at a temperature T1 ranging from 40°C to 160°C; sometimes at a temperature T1 ranging from 60°C to 140°C.
[0031 ] In some embodiments, in the process according to the invention, contacting the halogenated hydrocarbon with the sulfoxide containing resin is carried out with the halogenated hydrocarbon being in a liquid phase (L), in the bulk or as a solution (SO) in a solvent.
[0032] Generally, the sulfoxide containing resin is not soluble in the liquid phase (L). In some embodiments the sulfoxide containing resin is swollen by the liquid phase (L).
[0033] Therefore in some embodiments, the process according to the invention comprises the step a) of providing a liquid phase (L) consisting of liquid halogenated hydrocarbon in the bulk or consisting of a solution (SO) of the halogenated hydrocarbon in a solvent. This step a) comes before contacting the halogenated hydrocarbon with the sulfoxide containing resin.
[0034] Step a) is generally performed in a vessel such as a tank equipped with a stirring system and optionally a heating system.
[0035] When solvent is present, the amount of the halogenated hydrocarbon in the solution (SO) generally ranges from 10 wt % to 99 wt % with regards to the total weight of solution (SO) at 25°C.
[0036] When liquid halogenated hydrocarbon is used in the bulk, it is used as provided by manufacturers.
[0037] In some embodiments, a base is added to the liquid phase (L) in step a).
[0038] The base can be organic and is generally selected from bases containing at least one nitrogen atom and mixtures thereof.
[0039] For example, suitable organic base can be selected from the list consisting of guanidine bases like 1 ,5,7-Triazabicyclo 4.4.0 dec-5-ene (TBD) and 1 , 1 ,3,3- tetramethylguanidine (TMG), amidine bases like 1 ,8-Diazabicyclo(5.4.0)undec- 7-ene (DBU) and 1 ,5-Diazabicyclo(4.3.0)non-5-ene (DBN), 1 ,4- diazabicyclo[2.2.2]octane (DABCO), hexamethylenetetramine (HMTA), ethylenediamine (EDA), diethylenediamine (DEDA), triethylenediamine (TEDA), pyridine, imidazole, benzimidazole and mixtures thereof.
[0040] When a base is used in the liquid phase (L), the molar ratio of base to the targeted halogen atom (X) present in halogenated hydrocarbon generally ranges from 0.1 to 5; often from 0.5 to 3; sometimes from 1 to 2. By targeted halogen atom (X) is meant: the halogen atom that is aimed to be removed by dehydrohalogenation.
[0041 ] In the step a) of the process according to the invention, the liquid phase (L) is generally heated at a temperature T1 ranging from 40°C to 200°C and maintained at this temperature.
[0042] In some embodiments, the liquid phase (L) obtained in a) is heated at a temperature T1 ranging from 40°C to 160°C; sometimes at a temperature T1 ranging from 60°C to 140°C.
[0043] Step a) can be conducted in a vessel equipped with stirring and heating systems and which can serve as a reservoir of the liquid phase (L) at the temperature T1 .
[0044] In some embodiments, contacting at a temperature T1 ranging from 40°C to 200 °C the halogenated hydrocarbon with the sulfoxide containing resin is
conducted by passing the liquid phase (L) through a column, packed with a sulfoxide containing resin, to obtain a liquid phase (L1 ). This is generally performed by injecting the liquid phase (L) in an inlet at one end of the column, using any mean well known by the skilled person to inject a liquid in a column, and recovery of a liquid phase (L1 ) in an outlet at the other end of the column. [0045] For example, injection of heated liquid phase (L) of step a) through the column can be performed using a peristaltic pump.
[0046] Generally, contacting the halogenated hydrocarbon with the sulfoxide containing resin is conducted at a pressure ranging from 1 bar to 100 bars; often ranging from 1 bar to 50 bars; sometimes ranging from 1 bar to 20 bars.
[0047] Generally, the residence time of the liquid phase (L) in the column ranges from 5 seconds to 1 hour. Often, the residence time of the liquid phase (L) in the column ranges from 1 minute to 30 minutes; sometimes from 5 minutes to 15 minutes.
[0048] A liquid phase (L1 ) wherein the halogenated hydrocarbon is completely, substantially completely or at least partially converted into the corresponding unsaturated hydrocarbon is recovered at the outlet of the column.
[0049] Dehydrohalogenation can be assessed by any technique well known by the person of ordinary skill in the art.
[0050] For example, dehydrohalogenation of the halogenated hydrocarbon can be assessed by monitoring the corresponding unsaturated hydrocarbon generation and/or the halogenated hydrocarbon disappearance in the liquid phase (L1 ) by connecting a HPLC line to the outlet of the column.
[0051 ] When partial conversion of the halogenated hydrocarbon is observed in (L1 ), the process can be reproduced until complete conversion.
[0052] In some embodiments, in the process according to the invention, contacting the halogenated hydrocarbon with the sulfoxide containing resin is carried out with the halogenated hydrocarbon being in a gas phase (G), in the bulk or in the presence of a gas carrier.
[0053] Therefore in some embodiments, the process according to the invention comprises the step a’) of providing a gas phase (G) consisting of gaseous
halogenated hydrocarbon in the bulk or consisting of a mixture of the halogenated hydrocarbon with a gas carrier. The gas carrier can be selected from inert gas such as nitrogen, argon and mixtures thereof. This step a’) comes before contacting the halogenated hydrocarbon with the sulfoxide containing resin.
[0054] The gas phase (G) may be obtained from liquid halogenated hydrocarbon by heating the same to a temperature above its boiling point at a given pressure.
[0055] In some embodiments, in the process according to the invention gaseous halogenated hydrocarbon is obtained from liquid halogenated hydrocarbon loaded into a reactor maintained at a temperature above its respective boiling point.
[0056] The term reactor is not limited and encompasses any vessel equipped with an inlet to feed with liquid and an outlet to recover gas, with heating system. The reactor may be set at reduced or high pressure.
[0057] In some embodiments gas phase (G) is obtained by mixing the gaseous halogenated hydrocarbon as obtained above with a gas carrier.
[0058] In some embodiments, contacting at a temperature T1 ranging from 40°C to 200 °C the halogenated hydrocarbon with the sulfoxide containing resin is conducted by passing the gas phase (G) through a column, packed with a sulfoxide containing resin, to obtain a gas phase (G1). This is generally performed by injecting the gas phase (G) in an inlet at one end of the column, using any means well known by the skilled person to inject a gas in a column, and recovery of a gas phase (G1 ) in an outlet at the other end of the column.
[0059] For example, injection of heated gas phase (G) of step a’) through the column can be performed using a peristaltic pump or a syringe pump.
[0060] In other examples, gaseous halogenated hydrocarbon is suitably co-injected with a carrier gas into the inlet of the column maintained at a temperature T1 above its respective boiling point generating the gas phase (G) in-situ.
[0061] In some embodiments liquid halogenated hydrocarbon is injected into the column maintained at a temperature T1 above its respective boiling point and is instantaneously moved to gaseous phase (G).
[0062] For example liquid halogenated hydrocarbon is suitably injected into the column maintained at a temperature T1 above its respective boiling point by cannulation with carrier gas.
[0063] In other examples liquid halogenated hydrocarbon is suitably injected into the column maintained at a temperature T1 above its respective boiling point using a pump, for example a syringe pump.
[0064] Still in other examples, liquid halogenated hydrocarbon is suitably co-injected with a carrier gas into the inlet of the column maintained at a temperature T1 above its respective boiling point generating the gas phase (G) in-situ.
[0065] When gas carrier is present, the amount of the halogenated hydrocarbon in the mixture generally ranges from 10 wt % to 99 wt % with regards to the total weight of the mixture.
[0066] Generally, contacting the halogenated hydrocarbon in the gas phase (G) with the sulfoxide containing resin is conducted at a pressure ranging from 1 bar to 100 bars; often ranging from 1 bar to 50 bars; sometimes ranging from 1 bar to 20 bars.
[0067] Generally, the residence time of the gas phase (G) in the column ranges from 5 seconds to 1 hour. Often, the residence time of the gas phase (G) in the column ranges from 1 minute to 30 minutes; sometimes from 5 minutes to 15 minutes.
[0068] A gas phase (G1 ) wherein the halogenated hydrocarbon is completely, substantially completely or at least partially converted into the corresponding unsaturated hydrocarbon is recovered at the outlet of the column.
[0069] Dehydrohalogenation can be assessed by any technique well known by the person of ordinary skill in the art.
[0070] For example, dehydrohalogenation of the halogenated hydrocarbon can be assessed by monitoring the corresponding unsaturated hydrocarbon generation and/or the halogenated hydrocarbon disappearance in the gas phase (G1 ) by connecting a GC line to the outlet of the column.
[0071 ] The nature of the materials composing the vessels and the column used in the present invention is not limited. However, the steps of the process according
to the invention are advantageously carried out in equipment capable of withstanding the conditions, especially due to the presence of HX at the temperature range required. This also applies for e.g. the peristaltic pump and other equipment.
[0072] For this purpose, materials are selected for the part in contact with the reaction mixture that are corrosion-resistant, such as the alloys based on molybdenum, chromium, cobalt, copper, manganese, titanium, zirconium, aluminum, carbon and tungsten, sold under the Hastelloy® brands or the alloys of nickel, chromium, iron and manganese to which copper and/or molybdenum are added, sold under the name Inconel® or MonelTM, and more particularly the Hastelloy C276 or Inconel 600, 625 or 718 alloys. Use may also be made of equipment consisting of or coated with a polymeric compound resistant to the corrosion of the reaction medium. Mention may in particular be made of materials such as PTFE (polytetrafluoroethylene or Teflon) or PFA (perfluoroalkyl resins).
[0073] Without being bonded to any theory, in the process according to the invention, the dehydrohalogenation, which occurs at low temperature and under mild conditions, is deemed to be catalyzed by the sulfoxide groups grafted onto the resin packed into the column. It is assumed that sulfoxide groups form some complexes with the polar groups of the perfluoroalkyl acid (PFAA) and/or of the perfluoroalkyl acid derivative that trigger the degradation of these perfluorinated compounds at relatively low temperature.
[0074] Any resin comprising sulfoxide groups is suitable for the process according to the invention. However, it is preferred that the resin is selected from polymers stable towards hydrolysis. Therefore generally a resin suitable for the present invention is free of hydrolysable groups such as ester, thioester, carbonate, thiocarbonate, amide, thioamide, imide, carbamate, thiocarbamate, urea and thiourea groups.
[0075] The sulfoxide-containing resin generally comprises a plurality of grafted sulfoxide groups and is free of hydrolysable groups such as those above described.
[0076] The sulfoxide-containing resin can be selected from polymers bearing sulfoxide groups in the polymer backbone, polymers bearing pending sulfoxide groups and mixtures thereof.
[0077] In some embodiments, the sulfoxide-containing resin is selected from crosslinked polymers bearing sulfoxide groups in the polymer backbone, crosslinked polymers bearing pending sulfoxide groups and mixtures thereof.
[0078] Polymers bearing sulfoxide groups in the polymer backbone, or main chain polysulfoxides, are for example polyethylene sulfoxide (PESO) or polypropylene sulfoxide (PPSO) as represented below.
[0079] Polyethylene sulfoxide (PESO) polypropylene sulfoxide (PPSO)
[0080] Polyethylene sulfoxide (PESO) and polypropylene sulfoxide (PPSO) can be prepared by selective oxidation of the corresponding polyethylene sulfide or polypropylene sulfide obtained by anionic ring-opening polymerization of ethylene sulfide or propylene sulfide respectively. Copolymers can be obtained starting from mixtures of ethylene sulfide and propylene sulfide.
[0081 ] In some embodiments, the polymers bearing sulfoxide groups in the polymer backbone are polymers or copolymers comprising a plurality of at least one of the repeat units of formulae (A) and (B) below:
[0082]
[0083] In some embodiments, polymers bearing pending sulfoxide groups, or side group polysulfoxides, can be selected from the group consisting of
homopolymers and copolymers comprising a plurality of at least one repeat unit of formulae (C) to (E) below:
wherein R, R’ and R”, which can be the same or different, are C1 -C6 alkyl groups.
[0084] For example, suitable copolymers bearing pending sulfoxide can be the copolymer (I) and the copolymer (II) below. These copolymers can be synthesized via a first step of free radical polymerization of ethylene or propylene, styrene and chlorobenzyl styrene to obtain a copolymer bearing chlorobenzyl groups. Then the sulfidation of the chlorobenzyl is performed followed by oxidation of the resulting sulfide to give copolymers bearing pending sulfoxide. A detailed example will be explained in the experimental part.
copolymer (II)
[0085] Crosslinked copolymer can be obtained e.g. by performing a first step of free radical polymerization of ethylene and/or propylene, styrene and chloromethyl styrene in the presence of divinylbenzene to obtain a crosslinked copolymer bearing chlorobenzyl groups that can be further modified to sulfide then to sulfoxide groups.
[0086] Still suitable copolymers bearing pending sulfoxide can be synthesized via a first step of free radical polymerization of styrene and chloromethyl styrene optionally in the presence of divinylbenzene.
[0087] In another aspect, the present application relates to a column packed with a sulfoxide containing resin as previously described.
[0088] Still in another aspect, the present application relates to the use of a column packed with a sulfoxide containing resin for conducting the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon.
[0089] The sulfoxide containing resin as previously described is suitable for conducting the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom and at least one hydrogen atom on vicinal carbon atoms in columns packed therewith.
[0090] Finally in another aspect, the present application relates to an industrial set up comprising a column packed with a sulfoxide containing resin for conducting the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon.
[0091 ] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
[0092] The invention will be now described with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.
Examples
[0093] Raw materials
[0094] Propylene and nitrobenzene were obtained from Sigma Aldrich.
[0095] Chloromethylstyrene and styrene were obtained from Merck Millipore.
[0096] Di-tert-butylperoxide (DTBP) free radical initiator was obtained from Reagenti Carlo Erba.
[0097] All these materials were used without further purification.
[0098] Difluoro{[2,2,4,5-tetrafluoro-5-(trifluoromethoxy)-1 ,3-dioxolan-4-yl]oxy}acetic acid (cC6O4) was synthesized internally according WO 2010/003929 A1.
[0099] Synthesis of copolymer bearing pending sulfoxide groups
[00100] Propylene (2 g) was condensed from a glass vacuum manifold rack into an AIS 1-316 high pressure reactor cooled in liquid nitrogen and equipped with inlet and outlet valves, a magnetic stir bar, an internal thermocouple, a pressure transducer connected to a Nanodac temperature and pressure digital multifunction reader. Following propylene filling, four vacuum/N2 cycles were run to ensure an O2 free atmosphere. The pressure reactor was left under vacuum and cooled in liquid nitrogen. A solution of 4-chloromethylstyrene (20 mol % vs propylene) and a solution of DTBP (5 mol% vs 4-chloromethylstyrene) in 10 mL nitrobenzene were then siphoned into the reactor and the reactor was warmed to room temperature.
[00101 ] The reactor was then fit into a steel heating mantle connected to temperature control equipped with 2 thermocouples connected to the Nanodac digital multifunction reader. The reactor was heated to 140°C for 8 hrs, then cooled to room temperature and the contents poured into a round-bottomed flask. The solvent was removed by distillation under vacuum and a white waxy substance was obtained. The wax was washed several times in diethyl ether in order to remove unreacted monomers.
[00102] After vacuum rotary evaporation at 50°C, the plastic-like wax was analyzed by by semi-quantitative X-ray fluorescence elemental analysis (Cl as analyte) in order to determine the Cl content by comparison with a matrix of a known concentration of 4-chloromethylstyrene. Approximately 5 mol% of grafted 1 - ethyl-4-chlorobenzyl derivative was found to be incorporated.
[00103] A reaction pathway involving styrene is represented in scheme 1 below:
[00105] The chlorobenzyl derivative was suspended in toluene (50 mL) and approximately an equimolar amount of sodium methyl thiolate in a 20 wt % solution of NaOH in water was added along with tetrabutylammonium
hydroxide (4 mol % vs chlorobenzyl group) as phase transfer catalyst and the biphasic mixture was stirred at 60°C for 4 days. After cooling to room temperature the toluene suspension phase was separated and washed with distilled water until neutral pH was reached. The waxy plastic was then washed with diethyether to remove all left-over organics and dried under vacuum with a rotary evaporator. Semi-quantitative X-ray fluorescence elemental analysis (S as analyte) was used to check that the SN2 had occurred.
[00106] Conversion to the sulfoxide was achieved by using an excess of H2O2 (15% w/w) at 30°C in CH2CI2 overnight to ensure only partial oxidation avoiding the following oxidation to sulfoxide. The oxidation mixture was then washed with an excess of distilled water, followed by a washing with diethylether and rotavapor evaporation at 60°C under vacuum. FT-IR (KBr) of the resulting plastic-like wax showed the sulfoxide band at 1030 - 1040 cm-1 and disappearance of the 1240 cm-1 band of C-S-C band (thio-ether). Thioether conversion = 100% and the final isolated yield was approximatively 10 mol%.
[00107] Example 1
[00108] The efficiency of grafted sulfoxide (grafted DMSO) was tested by performing a known reaction carried out by free DMSO and namely the oxidation of ethanol to acetaldehyde by the Swern Oxidation. Although grafted DMSO is not intended to be used for such a reaction, it was selected solely for the purpose of demonstrating that the DMSO synthon was actually bound to the resin and available as catalytic site. Oxalyl chloride (100 mg 0.788 mmoles = 1.58 meq) was placed in a round-bottom flask containing 5 mL of dry diethyl ether as the inert solvent. The reactor was equipped with a reflux condenser, a magnetic stirrer and an internal thermocouple attached to a Nanodac temperature reader. The grafted DMSO (1 g = approximately 1 mmol grafted DMSO) was placed in contact with the oxalyl chloride/diethyl ether solution and the mixture was cooled to -78°C with stirring in a Dewar containing a dry ice/acetone bath. Once the mixture turned pink, dry ethanol (23 mg = 27 pL = 0.5 mmol) was added with a micro-syringe and the mixture was kept at -78°C with stirring for 10 min. Once the solution turned a pale yellow, dry triethylamine (50 mg = 72
pL = 0.5 mmol) was added employing a micro-syringe. A slight exothermicity (+5°C) was observed at this time. Once the internal T returned to -78°C the solution was warmed to -30°C and then an aliquot was injected in a GC equipped with a 25 m wide boar (0.54 mm) CP-Sil 8CB column. The acetaldehyde yield was calculated to be 35 %.
[00109] Example 2 (comparative example).
[00110] The same reaction described in Example 1 was carried out employing free DMSO (1 mmol = 39 mg = 35 pL). The calculated acetaldehyde yield was 50 %.
[00111] Example 3 (comparative example).
[00112] The same reaction described in Example 1 was repeated substituting grafted DMSO with the polystyrene/polypropylene polymer matrix. No acetaldehyde was observed.
[00113] Table 1: evaluation of grafted DMSO as catalyst for Swern Oxidation
Claims
Claim 1 . A process for the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon, said process comprising contacting at a temperature T1 ranging from 40°C to 200 °C the halogenated hydrocarbon with a sulfoxide containing resin, optionally in the presence of a base; wherein the sulfoxide containing resin comprises a plurality of grafted sulfoxide groups and is free of hydrolysable groups; and wherein halogen atom (X) is selected from F, Cl, Br and I, preferably from F and Cl and more preferably is Cl.
Claim 2. The process according to claim 1 , wherein the halogenated hydrocarbon is selected from the list consisting of 1 ,1 ,2-trichloroethane, 1 ,2-dichloroethane, 1- chloro-1 ,1 -difluoroethane and 1-bromo-1 ,1 -difluoroethane.
Claim 3. The process according to claim 1 or 2, wherein contacting the halogenated hydrocarbon with the sulfoxide containing resin is carried out by passing the halogenated hydrocarbon, optionally in the presence of a base, through a least one column packed with the sulfoxide containing resin and thermostated at the temperature T1 ranging from 40°C to 200°C.
Claim 4. The process according to any one of claims 1 to 3, wherein contacting the halogenated hydrocarbon with the sulfoxide containing resin is carried out with halogenated hydrocarbon being in a liquid phase (L), in the bulk or as a solution (SO) in a solvent..
Claim 5. The process according to claim 4, wherein the solvent is an organic solvent selected from the group consisting of ketones, sulfoxides, like dimethylsulfoxide, sulfones, like dimethylsulfone, amides, like N,N- dimethylformamide, N,N-dimethylacetamide, pyrrolidones, like N-
methylpyrrolidone, N-ethylpyrrolidone, ethers, like tetraethyleneglycol dimethyl ether (tetraglyme) and mixtures thereof.
Claim 6. The process according to claim 4 or 5, wherein the base is selected from organic bases containing at least one nitrogen atom and mixtures thereof; preferably wherein the base is selected from the list consisting of guanidine bases like 1 ,5,7-Triazabicyclo 4.4.0 dec-5-ene (TBD) and 1 ,1 ,3,3-tetramethylguanidine (TMG), amidine bases like 1 ,8-Diazabicyclo(5.4.0)undec-7-ene (DBU) and 1 ,5- Diazabicyclo(4.3.0)non-5-ene (DBN), 1 ,4-diazabicyclo[2.2.2]octane (DABCO), hexamethylenetetramine (HMTA), ethylenediamine (EDA), diethylenediamine (DEDA), triethylenediamine (TEDA), pyridine, imidazole, benzimidazole and mixtures thereof.
Claim 7. The process according to any one of claims 4 to 6, wherein contacting the halogenated hydrocarbon with the sulfoxide containing resin is carried out at a pressure ranging from 1 to 50 bars.
Claim 8. The process according to any one of claims 1 to 3, wherein contacting the halogenated hydrocarbon with a sulfoxide containing resin is carried out with the halogenated hydrocarbon being in a gas phase (G), in the bulk or in the presence of a gas carrier.
Claim 9. The process according to claim 8, wherein contacting the halogenated hydrocarbon with the sulfoxide containing resin is carried out at a pressure ranging from 1 to 100 bars.
Claim 10. The process according to any one of the preceding claims, wherein contacting the halogenated hydrocarbon with the sulfoxide containing resin or passing the halogenated hydrocarbon through the at least one column packed with
the sulfoxide containing resin is conducted during a period of time ranging from 5 seconds to 5 hours.
Claim 11 . The process according to any one of the preceding claims wherein the sulfoxide containing resin is selected from polymers bearing sulfoxide groups in the polymer backbone, polymers bearing pending sulfoxide groups and mixtures thereof.
Claim 12. The process according to claim 11 wherein polymer bearing sulfoxide groups in the polymer backbone is selected from the group consisting of polymers and copolymers comprising a plurality of at least one of the repeat units of formulae (A) and (B) below:
Claim 13. The process according to claim 11 wherein polymer bearing pending sulfoxide groups is selected from the group consisting of polymers and copolymers comprising a plurality of at least one of the repetitive unit of formulae (C) to (E) below:
wherein R, R’ and R”, which can be the same or different, are C1-C6 alkyl groups.
Claim 14. The process according to any one of the preceding claims, wherein the sulfoxide containing resin is selected from crosslinked polymers.
Claim 15. A column packed with a sulfoxide containing resin, wherein the nonsulfoxide containing resin is selected from polymers bearing sulfoxide groups in the polymer backbone, polymers bearing pending sulfoxide groups and mixtures thereof, wherein polymer bearing sulfoxide groups in the polymer backbone is selected from the group consisting of polymers and copolymers comprising a plurality of at least one of the repeat units of formulae (A) and (B), and wherein polymer bearing pending sulfoxide groups is selected from the group consisting of polymers and copolymers comprising a plurality of at least one of the repetitive unit of formulae (C) to (E) and is free of hydrolysable groups.
Claim 16. Use of a column packed with a sulfoxide containing resin for conducting the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon.
Claim 17. Industrial set up comprising a column packed with a sulfoxide containing resin, wherein the non- sulfoxide containing resin is selected from polymers bearing sulfoxide groups in the polymer backbone, polymers bearing pending sulfoxide groups and mixtures thereof, wherein polymer bearing sulfoxide groups in the polymer backbone is selected from the group consisting of polymers and copolymers comprising a plurality of at least one of the repeat units of formulae (A) and (B), and wherein polymer bearing pending sulfoxide groups is selected from the group consisting of polymers and copolymers comprising a plurality of at least one of the repetitive unit of formulae (C) to (E), for conducting the dehydrohalogenation of a halogenated hydrocarbon comprising at least one halogen atom (X) and at least one hydrogen atom on vicinal carbon atoms to yield the corresponding unsaturated hydrocarbon.
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|---|---|---|---|
| EP24187597.0 | 2024-07-10 | ||
| EP24187597 | 2024-07-10 |
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| WO2026012766A1 true WO2026012766A1 (en) | 2026-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/EP2025/068158 Pending WO2026012766A1 (en) | 2024-07-10 | 2025-06-26 | Process for the dehydrohalogenation of halogenated hydrocarbons |
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