WO2010007006A1 - Process to purify dialkyl sulfides - Google Patents

Process to purify dialkyl sulfides Download PDF

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Publication number
WO2010007006A1
WO2010007006A1 PCT/EP2009/058848 EP2009058848W WO2010007006A1 WO 2010007006 A1 WO2010007006 A1 WO 2010007006A1 EP 2009058848 W EP2009058848 W EP 2009058848W WO 2010007006 A1 WO2010007006 A1 WO 2010007006A1
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WO
WIPO (PCT)
Prior art keywords
metal
dialkyl
sulfide
dialkyl sulfide
alkali
Prior art date
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Ceased
Application number
PCT/EP2009/058848
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English (en)
French (fr)
Inventor
Elizabeth Burkhardt
Kevin Neigh
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BASF SE
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BASF SE
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Filing date
Publication date
Priority to CA2730707A priority Critical patent/CA2730707C/en
Priority to EP09780449.6A priority patent/EP2315743B1/en
Priority to SI200931970T priority patent/SI2315743T1/sl
Priority to RU2011105242/04A priority patent/RU2515986C2/ru
Priority to CN200980127616.2A priority patent/CN102099332B/zh
Priority to DK09780449.6T priority patent/DK2315743T3/da
Application filed by BASF SE filed Critical BASF SE
Priority to US13/003,587 priority patent/US8586796B2/en
Priority to JP2011517882A priority patent/JP5587310B2/ja
Priority to ES09780449T priority patent/ES2727702T3/es
Publication of WO2010007006A1 publication Critical patent/WO2010007006A1/en
Anticipated expiration legal-status Critical
Priority to US14/057,109 priority patent/US9073831B2/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26—Separation; Purification; Stabilisation; Use of additives
    • C07C319/28—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B57/00—Separation of optically-active compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
    • C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides

Definitions

  • the invention relates to new processes to purify dialkyl sulfides, the purified dialkyl sulfides obtainable by these processes and to methods of using these purified dialkyl sulfides. Moreover, the invention relates to a process to prepare dialkyl sulfide bo- rane complexes of high purity, the dialkyl sulfide borane complexes obtainable by this process and to a process for enantioselective reductions employing these dialkyl sulfide borane complexes of high purity as reducing agent.
  • Dialkyl sulfides are versatile reagents for organic syntheses. Moreover, lower dialkyl sulfides are often employed as valuable solvents. Most organic sulfides with low molecular mass have intense unpleasant odors, which in many cases is further deteriorated through the presence of sulfur-containing impurities (K.-M. Roy, "Thiols and Organic Sulfides", Ullmann ' s Encyclopedia of Industrial Chemistry, 7 th Ed., pages 1 to 28, Wiley-VCH Verlag GmbH & Co. KGaA 2008).
  • DMS di- methyl sulfide
  • impurities such as carbon disulfide, carbonyl sulfide, methyl thiol, dimethyldisulfide, hydrogen sulfide and other sulfurous compounds at low levels.
  • concentration of these impurities is less than one percent and for some compounds is less than 200 ppm
  • the odor of the impurities gives the DMS a vile stench of rotten eggs, cabbage and skunk.
  • Some sulfur compounds having the odor of garlic or onions may also contribute to the odor.
  • DMS of high purity has the odor of corn or a grassy meadow (D. J. Rowe, Perfumer & FIa- vorist 1998, Vol. 23, pages 9 to 14).
  • DMS is used as an anti-coking agent in petroleum steamcrackers and as raw mate- rial to make the solvent dimethylsulfoxide (DMSO).
  • DMS is also used as a solvent and for coordination to metal compounds or other Lewis acids, i.e. borane compounds.
  • Dimethyl sulfide borane (DMSB) is a stable concentrated (10M) form of borane (BH 3 ) utilized in the pharmaceutical industry for the reduction of carbonyl compounds, imines, and hydroboration of double bonds in alkenes or alkynes.
  • the un- pleasant odor of DMSB made from impure DMS can be noticed at very low levels in production operations and can drift in the wind into communities.
  • US Patent 6,736,879 discloses an absorption method to remove carbon disulfide from dimethyl sulfide.
  • the absorption media is an activated alumina treated with alkali metal and alkaline earth compounds and can be regenerated.
  • absorption of the impurities in dialkyl sulfides may remove some contaminates but will not completely remove the variety of impurities due to the reversibility of the absorption process.
  • dimethyl sulfide and dimethyldisulfide have used odor- masking compounds to give the mixture a more pleasant odor (US 5,559,271 , US 6,639,110).
  • the compounds used have functional groups that are reactive with bo- rane and therefore cannot be used in the application of DMSB preparation.
  • High purity DMS is a desirable commercial product suitable as flavoring agent or solvent as well as low odor compounds made from it, i.e. DMSO or DMSB.
  • Selective removal of undesirable components, while leaving the desired dimethyl sulfide, is not adequately addressed by current literature.
  • oxidation methods are destructive to all components of the mixture.
  • low odor dialkyl sulfides have been developed that lack major malodorous impurities and methods of using these low odor dialkyl sulfides to prepare low odor products or as low odor solvent.
  • dialkyl sulfide borane complexes of high purity together with a process for their preparation have been developed and a improved process for enantioselec- tive reductions employing these dialkyl sulfide borane complexes of high purity as reducing agent was found.
  • One embodiment of the present invention is a process to purify dialkyl sulfides comprising the step of bringing a dialkyl sulfide into contact with at least one base and/or at least one alkali or alkaline earth metal, wherein the base is a metal alcoholate, a metal oxide, a metal or alkylammonium hydroxide, a metal or alkylammonium carbonate, a metal enolate, a metal amide or a metal hydride, wherein the metal is selected from the group, consisting of the alkali metals, the alkaline earth metals and the metals of the groups Ilia to Villa, Ib and lib.
  • a preferred embodiment of the present invention is a process to purify dialkyl sulfides comprising the step of bringing a dialkyl sulfide into contact with at least one base and at least one alkali or alkaline earth metal.
  • a dialkyl sulfide is a compound with the chemical formula R-S-R ' , wherein R and R ' are independent from each other C1-C18 alkyl, C3-Ci 4 cycloalkyl, substituted CrCi 8 alkyl, substituted C 3 -Ci 4 cycloalkyl or R and R ' are connected as a divalent hydrocarbon moiety, that may contain further sulfur, oxygen, or nitrogen atoms, which together with the sulfur atom forms a cyclic dialkyl sulfide structure.
  • dialkyl sulfide is dimethyl sul- fide, diethyl sulfide, methyl ethyl sulfide, methyl isopropyl sulfide or thioxane.
  • Ci - Ci ⁇ alkyl denotes a branched or an unbranched saturated hydrocarbon group comprising between 1 and 18 carbon atoms; examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- butyl, tert-butyl, amyl, isoamyl, sec-amyl, 1 ,2-dimethylpropyl, 1 ,1-dimethylpropyl, hexyl, 4-methylpentyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 1 ,1- dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3- dimethylbutyl, 1 ,2,2-trimethylpropyl, 1 ,1 ,2-trimethylpropyl, heptyl, 5-methylhexyl, 4-methylpentyl, 1
  • alkyl groups methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, iso- amyl, sec-amyl, 1 ,2-dimethylpropyl, 1 ,1-dimethylpropyl, hexyl and octyl.
  • C 3 - Ci 4 cycloalkyl denotes a saturated hydrocarbon group comprising between 3 and 14 carbon atoms including a mono- or polycyclic structural moiety. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooc- tyl, cyclononyl or cyclodecyl. Preferred are the cycloalkyl groups cyclopropyl, cyclopentyl and cyclohexyl.
  • substituted CrCi 8 alkyl or "substituted C 3 -Ci 4 cycloalky” denotes an alkyl group or a cycloalkyl group as defined above in which at least one hydrogen atom is replaced by a fluorine atom.
  • cyclic dialkyl sulfides include thietane, thiolane, thioxane, 1 ,3-dithiane, 1 ,4-dithiane and 2-methyl-1 ,3-dithiane.
  • dialkyl sulfide used as a start- ing material should have a purity of at least 95 wt.-%, preferably at least 99 wt.-%.
  • dialkyl sulfide and the at least one base and/or at least one alkali or alkaline earth metal are brought into contact for a time in the range from about 1 second to about 24 hours, most pre- ferred in the range between 1 minute and 3 hours.
  • the dialkyl sulfides is brought into contact with at least one base, which is a metal alcoholate, a metal oxide, a metal or alkylammonium hydroxide, a metal or alkylammonium carbonate, a metal enolate, a metal amide or a metal hydride.
  • the metal can be selected from the group, consisting of the alkali metals, the alkaline earth metals and the metals of the groups Ilia to Villa, Ib and Mb. Preferred are the alkali metals, magnesium, calcium, barium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc.
  • a metal alcoholate comprises at least one alkoxy group that can be derived from any branched or unbranched aliphatic alcohol.
  • suitable metal alcoholates include potassium alcoholates, sodium alcoholates, lithium alcoholates, magnesium alcoholates, zinc alcoholates and tita- nium alcoholates derived from methanol, ethanol or t-butanol.
  • dialkyl sulfides is brought into contact with at least one alkali or alkaline earth metal.
  • alkali or alkaline earth metal can also be employed as mixtures with each other (i.e. as alloys) or with mercury (i.e. as amal- gams).
  • Preferred are dispersions of metals as well as metals on a supporting media such as alumina, silica, diatomaceous earth, graphite or other common mineral compositions. Most preferred is the use of alkali metals, especially of sodium- potassium alloys.
  • the dialkyl sulfide is brought into contact with a metal alcoholate and optionally with at least one alkali or alkaline earth metal.
  • the dialkyl sulfides is brought into contact with at least one base and with at least one alkali or alkaline earth metal consecutively in separate steps. In a preferred embodiment of the present invention the dialkyl sulfides is brought into contact with at least one base and with at least one alkali or alkaline earth metal simultaneously in one step.
  • dialkyl sulfide is brought into contact with potassium tert.-butoxide and a sodium-potassium alloy.
  • the process of the present invention can be carried out in the liquid or in the gas phase.
  • the method of choice for high throughput would be to subject gaseous dialkyl sulfide to a fixed bed containing a metal and a base on a supporting media to allow for sufficient contact time in order to irreversible remove the malodorous components from the dialkyl sulfide.
  • CS2 dialkyl sulfides
  • DMS dimethyl sulfide
  • Reaction of carbon disulfide with a metal alcoholate generates a xanthate salt (Dunn, A.D.; Ru- dorf, W. Carbon Disulphide in Organic Chemistry; Ellis Horwood: Chichester 1989, p. 316.), but this reaction is reversible under distillation conditions.
  • xanthate salt with an electrophile converts the salt to the xanthate ester which is stable and can easily be separated from the dialkyl sulfide by distillation. Since any thioate salt will also react with the electrophile to give the corresponding (and unde- sired) dialkyl sulfide, the electrophile should be chosen such that the products are non-volatile or high boiling. Therefore, another embodiment of the present invention is a process to purify dialkyl sulfides comprising the steps of
  • a dialkyl sulfide into contact with at least one base and/or at least one alkali or alkaline earth metal, wherein the base is a metal alcoholate, a metal oxide, a metal or alkylammonium hydroxide, a metal or alkylammonium carbonate, a metal enolate, a metal amide or a metal hydride, wherein the metal is selected from the group, consisting of the alkali metals, the alkaline earth metals and the metals of the groups Ilia to Villa, Ib and Mb, and
  • step b) reacting the product of step a) with an electrophile
  • dialkyl sulfide is brought into contact in step a) with a metal alcoholate and optionally with at least one alkali or alkaline earth metal.
  • electrophile any organic halide, methanesulfonate, thfluormethanesulfonate, p- toluenesulfonate and the like can be used.
  • the organic residue of the electrophile should have a high molecular mass in order to generate high-boiling products.
  • electrophiles suitable for the purification of low-boiling dialkyl sulfides include octyl bromide, benzyl bromide and benzyl chloride.
  • the new processes disclosed in this invention provide easy access to low odor dialkyl sulfides, which are of great value for the production of low odor compounds made from it, e. g. dimethyl sulfoxide or dimethyl sulfide borane complex from dimethyl sulfide.
  • Another embodiment of the present invention is the dialkyl sulfide obtainable by one of the processes disclosed above.
  • dialkyl sulfides In the dialkyl sulfides according to the invention the content of each of the impurities carbon disulfide, methanethiol and dimethyldisulfide is below 0.01 % wt. respectively.
  • Still another embodiment of the present invention is the method of using these low odor dialkyl sulfides to prepare low odor products or as a low odor solvent.
  • a preferred embodiment of the present invention is a method of using purified dialkyl sulfides to prepare dialkyl sulfide borane complexes of high purity.
  • An even more preferred embodiment of the present invention is a method of using purified dimethyl sulfide to prepare dimethyl sulfide borane (DMSB) of high purity.
  • DMSB dimethyl sulfide borane
  • a dialkyl sulfide into contact with at least one base and/or at least one alkali or alkaline earth metal, wherein the base is a metal alcoholate, a metal oxide, a metal or alkylammonium hydroxide, a metal or alkylammo- nium carbonate, a metal enolate, a metal amide or a metal hydride, wherein the metal is selected from the group, consisting of the alkali metals, the alkaline earth metals and the metals of the groups Ilia to Villa, Ib and Mb of the periodic table of elements, and
  • step b) optionally reacting the product of step a) with an electrophile and distilling out the dialkyl sulfide, and
  • step c) reacting the dialkyl sulfide purified according to step a) and optionally step b) with diborane.
  • a preferred embodiment of the present invention is a process to prepare dimethyl sulfide borane (DMSB) of high purity by the process described above wherein di- methyl sulfide is employed as dialkyl sulfide.
  • DMSB dimethyl sulfide borane
  • the reaction of purified dialkyl sulfide with diborane according to step c) of the process described above is usually carried out at temperatures between -10 and +50 0 C, preferrably at ambient temperature.
  • Diborane is preferably employed in gaseous form and the reaction is preferably carried out in a pressurized vessel.
  • Another embodiment of the present invention is the dialkyl sulfide borane complex of high purity obtainable by the process disclosed above.
  • dialkyl sulfide borane complexes the content of each of the impurities carbon disulfide, methanethiol and dimethyldisulfide is below 0.01 % wt. respectively. It was found that the enantiomeric excess obtained in enantioselective reductions with dialkyl sulfide boranes as reducing agent is higher with dialkyl sulfide borane complexes of high purity according to the invention compared with regular dialkyl sulfide borane complexes. This improvement is due to the lack of impurities like di- methyldisulfide (DMDS) or alkyl thiols (as shown by addition experiments, cf. Example 3) that are effectively removed by the purification processes disclosed above.
  • DMDS di- methyldisulfide
  • alkyl thiols as shown by addition experiments, cf. Example 3
  • dialkyl sulfide borane complexes of high purity is very advantageous because it helps to avoid purification steps.
  • another embodiment of the present invention is a process for enantiose- lective reductions which comprises using as reducing agent a dialkyl sulfide borane complex of high purity according to the invention.
  • Enantioselective reductions with dialkyl sulfide boranes as reducing agent are usually carried out in the presence of chiral boron-containing catalysts like tetrahydro-1 - methyl-3,3-diphenyl-1 H,3H-pyrrolo[1 ,2-c][1 ,3,2]oxazaborole (known as the (R)- or (S)-MeCBS oxazaborolidine reagent, see Corey, E.J.; HeIaI, C. J. Angew. Chem. Int. Ed.
  • the enantioselective reduction is the reduction of a prochiral ketone or imine.
  • Impure dimethyl sulfide (about 99.0% DMS, Chevron-Phillips) was stirred with various re- agents for 1 hour at ambient temperature in the liquid phase. Based on odor detection by (4) human volunteers, the odor after contact with the reagents was determined and related to a particular known odor.
  • the NaK and KTB treated sample was distilled from the solids and remaining unre- acted NaK.
  • the DMS distillate (entry 6) still had a slight odor of carbon disulfide. Dis- tillation of the DMS overcomes the problem of dissolved basic compounds, however due to the reversible nature of the reaction of carbon disulfide and base, the odor of distilled DMS had a hint of CS2 odor.
  • an electrophile bromooctane, benzyl bromide, benzyl chloride
  • Table 2 Analytical data (GC/MS) for dimethyl sulfides after different treatments. All figures are % wt.. DMS is dimethyl sulfide, CS2 is carbon disulfide, DMDS is dimethyldisulfide, MeSH is methanethiol, EtSMe is ethyl methyl sulfide, OctBr is 1 -bromooctane, BnCI is benzyl chloride and BnBr is benzyl bromide. Traces of acetone were from cleaning of the syringe between samples.
  • High purity DMSB was prepared as a 10M solution by addition of gaseous diborane at ambient temperature to DMS that has been purified according to the procedure disclosed in Table 2, Entry #4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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PCT/EP2009/058848 2008-07-15 2009-07-10 Process to purify dialkyl sulfides Ceased WO2010007006A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US13/003,587 US8586796B2 (en) 2008-07-15 2009-07-10 Process to purify dialkyl sulfides
EP09780449.6A EP2315743B1 (en) 2008-07-15 2009-07-10 Process to purify dialkyl sulfides
SI200931970T SI2315743T1 (sl) 2008-07-15 2009-07-10 Postopek čiščenja dialkil sulfidov
RU2011105242/04A RU2515986C2 (ru) 2008-07-15 2009-07-10 Способ очистки диалкилсульфидов
CN200980127616.2A CN102099332B (zh) 2008-07-15 2009-07-10 提纯二烷基硫醚的方法
CA2730707A CA2730707C (en) 2008-07-15 2009-07-10 Purification of dialkyl sulfides with basic metal alcoholates and/or alkali or alkaline earth metals
ES09780449T ES2727702T3 (es) 2008-07-15 2009-07-10 Procedimiento para purificar sulfuros de dialquilo
DK09780449.6T DK2315743T3 (da) 2008-07-15 2009-07-10 Fremgangsmåde til oprensning af dialkylsulfider
JP2011517882A JP5587310B2 (ja) 2008-07-15 2009-07-10 ジアルキルスルフィドの精製方法
US14/057,109 US9073831B2 (en) 2008-07-15 2013-10-18 Process to purify dialkyl sulfides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8086808P 2008-07-15 2008-07-15
US61/080868 2008-07-15

Related Child Applications (2)

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US13/003,587 A-371-Of-International US8586796B2 (en) 2008-07-15 2009-07-10 Process to purify dialkyl sulfides
US14/057,109 Division US9073831B2 (en) 2008-07-15 2013-10-18 Process to purify dialkyl sulfides

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WO2010007006A1 true WO2010007006A1 (en) 2010-01-21

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PCT/EP2009/058848 Ceased WO2010007006A1 (en) 2008-07-15 2009-07-10 Process to purify dialkyl sulfides

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US (2) US8586796B2 (https=)
EP (1) EP2315743B1 (https=)
JP (1) JP5587310B2 (https=)
KR (1) KR101617055B1 (https=)
CN (1) CN102099332B (https=)
CA (1) CA2730707C (https=)
DK (1) DK2315743T3 (https=)
ES (1) ES2727702T3 (https=)
RU (1) RU2515986C2 (https=)
SI (1) SI2315743T1 (https=)
WO (1) WO2010007006A1 (https=)

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CN103108862A (zh) * 2010-09-30 2013-05-15 阿肯马法国公司 用于制备二烷基二硫醚的方法
CN107857728A (zh) * 2017-11-20 2018-03-30 成都惟邦药业有限公司 一种利非司特中间体的合成方法
WO2020223035A1 (en) * 2019-04-29 2020-11-05 Chevron Phillips Chemical Company Lp Processes for removing carbon disulfide from symmetrical and asymmetrical sulfide product streams

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FR2994974B1 (fr) * 2012-08-30 2015-05-01 Arkema France Distillation reactive des dso
CN107674026B (zh) * 2017-11-03 2019-12-06 海化生命(厦门)科技有限公司 鲁索替尼中间体(3r)-3-(4-溴-1h-吡唑-1-基)-环戊烷基丙腈的制备方法
CN116283687A (zh) * 2022-09-07 2023-06-23 金川集团股份有限公司 一种二异戊基硫醚的合成工艺
US11945770B1 (en) * 2023-03-06 2024-04-02 Chevron Phillips Chemical Company Lp Catalytic processes and systems for alkyl sulfide purification

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