WO2001062719A1 - Oxydation selective de sulfures au moyen d"un systeme oxydant constitue de niobate de molibdenate de lithium et de peroxyde d"hydrogene - Google Patents

Oxydation selective de sulfures au moyen d"un systeme oxydant constitue de niobate de molibdenate de lithium et de peroxyde d"hydrogene Download PDF

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Publication number
WO2001062719A1
WO2001062719A1 PCT/KR2001/000252 KR0100252W WO0162719A1 WO 2001062719 A1 WO2001062719 A1 WO 2001062719A1 KR 0100252 W KR0100252 W KR 0100252W WO 0162719 A1 WO0162719 A1 WO 0162719A1
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Prior art keywords
sulfone
sulfoxide
mmol
sulfide
hydrogen peroxide
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PCT/KR2001/000252
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English (en)
Inventor
Sangho Koo
Kwanghyun Ahn
Songho Byeon
Jaedeuk Yang
Minkoo Ji
Soojin Choi
Original Assignee
Sangho Koo
Kwanghyun Ahn
Songho Byeon
Jaedeuk Yang
Minkoo Ji
Soojin Choi
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Publication date
Application filed by Sangho Koo, Kwanghyun Ahn, Songho Byeon, Jaedeuk Yang, Minkoo Ji, Soojin Choi filed Critical Sangho Koo
Priority to AU2001236161A priority Critical patent/AU2001236161A1/en
Publication of WO2001062719A1 publication Critical patent/WO2001062719A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B45/00—Formation or introduction of functional groups containing sulfur
    • C07B45/04—Formation or introduction of functional groups containing sulfur of sulfonyl or sulfinyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides

Definitions

  • the present invention relates to a process for preparing a sulfoxide or a sulfone, which is very important intermediate for synthesis of pharmaceuticals or natural compounds, via oxidation of a sulfide.
  • R and R * independently represent an alkyl. alkenyl. vinyl, allyl, propargyl or aryl group.
  • a sulfide compound is primarily oxidized to a sulfoxide compound, which is then further oxidized to a sulfone compound by oxidant.
  • oxidant oxidant
  • oxidants usable for oxidizing a sulfide include NaI0 , oxone, and the like.
  • oxidation of phenyl prenyl sulfide was tried in the presence of methyl alcohol solvent (Table 1 , Ex.3 - Ex.6) by the inventors.
  • sulfoxide compound [A] was mainly obtained regardless of the amount of the oxidant.
  • the selectivity was remarkable when using NaI0 4 as oxidant.
  • oxidation to sulfoxide [A] was easy, but oxidation to sulfone [B] was difficult, as was the reaction using hydrogen peroxide/acetic acid oxidant system.
  • MCPBA meta-chloroperbenzoic acid among the oxidants
  • epoxy sulfone compound [C] was obtained in 62% yield as well as sulfone compound [B] in 22% yield.
  • selective oxidation could be performed by controlling the amount of MCPBA, an oxidant having strong electrophilicity.
  • MCPBA an oxidant having strong electrophilicity.
  • excess amount of MCPBA by the use of excess amount of MCPBA, oxidation of the double bond as well as oxidation of sulfide was progressed to give epoxy sulfone compound [C].
  • MCPBA is employed in an excess amount, since the accurate amount cannot be evaluated as it is commercially merchandised in 60 - 80% purity. Especially, oxidation of the double bond should occur in case of performing the oxidation in a large scale. What is critical is that the MCPBA is expensive, and involves the problem of treating meta-chlorobenzoic acid as by-product, so that it can be hardly employed industrially.
  • sulfone [B] was very selectively obtained without providing oxidation of the double bond nor production of sulfoxide [A]
  • 64 - 74% of sulfoxide was obtained, but with about 10 - 20% of sulfone [B] as by-product.
  • the oxidant system consisting of metal oxide as catalyst and hydrogen peroxide as oxidant is suitable for oxidation of allylic sulfide having double bond of increased electron density by alkyl substituent(s), to sulfone.
  • the inventors evaluated the ability of selective oxidation of allylic sulfide having double bond of increased electron density due to extended conjugation to sulfoxide and sulfone. respectively, by using metal oxide as catalyst and controlling the amount of hydrogen peroxide as oxidant. Oxidation was attempted by using phenyl 3,7,1 1-trimethy 1-2,4,6, 10-dodecatetraenyl sulfide as the allylic sulfide, Nb 2 0 5 , Mo0 3 , V 2 0 5 , MeRe0 3 , Na 2 W0 4 , or the like as metal oxide catalyst, and 1 equivalent or 2 equivalents of hydrogen peroxide. The results are shown in Table 3.
  • the inventors paid intensive efforts to develop a process for selective oxidation of allylic sulfide comprising double bond(s) with high electron density due to many alkyl substituents or conjugation to the corresponding sulfoxide or sulfone, and eventually developed lithium molibdenate niobate(LiNbMo0 6 )-H 2 0 2 oxidant system.
  • the present invention provides a process of selective oxidation for preparing a sulfoxide or a sulfone compound from the corresponding sulfide by the use of an oxidant system consisting of LiNbMo0 6 as a composite metal oxide and H 2 0 2 as a quantitative oxidant, in the presence of alcoholic solvent and under the condition of controlling the amount of the quantitative oxidant.
  • a sulfoxide or a sulfone compound is synthesized in high yield under the condition of adding 1 equivalent or 2 or more equivalents (preferably, 3 equivalents) of hydrogen peroxide as quantitative oxidant in the presence of LiNbMo0 6 catalyst and alcohol solvent (preferably, methanol) at room temperature.
  • the quantitative oxidant is preferably added at 0°C.
  • R and R' are defined as above, and R" represents a lower alkyl group.
  • the inventors could obtain the corresponding sulfoxide or sulfone from a sulfide in high yield by using LiNbMo0 6 as composite metal oxide catalyst and hydrogen peroxide as quantitative oxidant under the condition of adding 1 equivalent or 2 equivalents of hydrogen peroxide, respectively, at 0°C to room temperature in the presence of alcohol solvent (preferably, methanol), to complete the invention.
  • alcohol solvent preferably, methanol
  • the object of the present invention is to provide a process for selective oxidation of a sulfide compound, especially, an allylic sulfide comprising double bond(s) with high electron density due to a multiple of alkyl substituents or conjugation, to the corresponding sulfoxide or sulfone.
  • the oxidant system according to the present invention LiNbMo0 6 - H 2 0 2 is very efficient on oxidation of an allylic sulfide having double bond of high electron density due to many alkyl substituents or conjugation, differently from MCPBA with high electrophilicity or hydrogen peroxide-acetic acid system.
  • the process provides selective synthesis of the desired sulfoxide or sulfone by controlling the amount of hydrogen peroxide as quantitative oxidant. without oxidizing the double bond to epoxy group.
  • an oxidant having low electrophilicity requires long reaction time owing to low reactivity in case of oxidation to a sulfide, and provides low selectivity of oxidation to sulfoxide or sulfone.
  • the composite metal catalyst LiNbMo0 6 employed in the present invention can be prepared with relative ease (Kar. T.; Choudhary, R. N. P.. Materials Lett. 1997,
  • the oxidant system LiNbMo0 6 - H 2 0 2 , is a very good oxidant system with excellent reactivity and selectivity to sulfoxide or sulfone in spite of its weak electrophilicity.
  • the oxidant system can provide the corresponding sulfoxide or sulfone compound from a sulfide within a few hours at ambient temperature with high selectivity and good yield.
  • the catalyst LiNbMo0 6 is added to the sulfide solution in an amount of 0.01 to 0.1 equivalent, preferably about 0.05 equivalent, and then 1 equivalent (in case of sulfoxide) or 2 or more equivalents (in case of sulfone) of about 30%) aqueous hydrogen peroxide solution is slowly added thereto.
  • reaction temperature is preferably maintained at 10°C or lower, more preferably at 0°C.
  • the oxidation is completed within about 1 hour in case of a sulfoxide, or about 4 hours in case of a sulfone.
  • the product can be purified by simply concentrating the obtained reaction mixture and subjected to a column chromatography. If in a large scale, the product is preferably worked-up by adding chloroform to the reaction mixture, washing with water, drying and concentrating, and then purified.
  • Example 1 Preparation of phenyl prenyl sulfoxide and sulfone
  • phenyl prenyl sulfide (0.71 g, 4.0 mmol) was dissolved in methanol (20 ml), and the solution was well stirred at 0°C.
  • methanol 20 ml
  • LiNbMo0 6 58 mg, 0.2 mmol
  • 30% aqueous hydrogen peroxide solution (1.20 g, 12.0 mmol
  • phenyl prenyl sulfide (0.60 g, 3.3 mmol) was dissolved in methanol (20 ml), and the solution was well stirred at room temperature.
  • methanol 20 ml
  • LiNbMoO ⁇ 49 mg, 0.2 mmol
  • 30% aqueous hydrogen peroxide solution 1.20 g, 12.0 mmol
  • chloroform 80 ml was added, and the mixture was well washed with distilled water (20 ml x 3), dried over anhydrous sodium sulfate, and filtered.
  • phenyl 3,7,1 l-trimethyl-2.4, 6.10-dodecatetraenyl sulfone was prepared as follows: In a mixture of benzene (30 ml) and methanol (70 ml), phenyl 3,7,1 l-trimethyl-2,4,6, 10-dodecatetraenyl sulfide having trans-/cis- ratio [on the double bond of C-2] of about 2.5: 1 (16.1 g, 51.5 mmol) was dissolved.
  • geranyl phenyl sulfone was prepared as follows: To a solution of geranyl phenyl sulfide (2.80 g, 1 1.4 mmol) dissolved in methanol (45 ml), was added LiNbMoO 6 (0.17 g, 0.60 mmol) as a catalyst, and then 30% aqueous hydrogen peroxide solution (3.86 g, 34.1 mmol) was slowly added thereto. After stirring at room temperature for 4 hours, the reaction mixture was worked up according to the same procedure of Example 1. to give the objective sulfone (2.68 g, 9.6 mmol. yield: 85%).
  • the NMR data of the obtained geranyl phenyl sulfone are shown below:
  • allyl phenyl sulfone was prepared as follows: To a solution of allyl phenyl sulfide (0.50 g, 3.4 mmol) dissolved in methanol (16 ml), was added LiNbMoO ⁇ (49 mg, 0.20 mmol) as a catalyst, and then 30% aqueous hydrogen peroxide solution (1.00 g, 10.1 mmol) was slowly added thereto. After stirring at room temperature for 4 hours, the reaction mixture was worked up according to the same procedure of Example 1. to give the objective sulfone (0.54 g, 3.0 mmol, yield: 85%>).
  • the NMR data of the obtained allyl phenyl sulfone are shown below:
  • crotyl phenyl sulfone was prepared as follows: To a solution of crotyl phenyl sulfide (1.64 g, 10.0 mmol) dissolved in methanol (50 ml), was added LiNbMoO 6 (0.15 g, 0.50 mmol) as a catalyst, and then 30% aqueous hydrogen peroxide solution (3.40 g, 30.0 mmol) was slowly added thereto. After stirring at room temperature for 4 hours, the reaction mixture was worked up according to the same procedure of Example 1, to give the objective sulfone ( 1.91 g, 9.7 mmol, yield: 97%o).
  • the NMR data of the obtained crotyl phenyl sulfone are shown below:
  • phenyl propargyl sulfone was prepared as follows: To a solution of phenyl propargyl sulfide ( 1.58 g, 10.7 mmol) dissolved in methanol (50 ml), was added LiNbMo0 6 (0.16 g, 0.50 mmol) as a catalyst, and then 30% aqueous hydrogen peroxide solution (3.60 g, 32.0 mmol) was slowly added thereto. After stirring at room temperature for 4 hours, the reaction mixture was worked up according to the same procedure of Example 1, to give the objective sulfone (1.62 g, 9.0 mmol, yield: 84%>).
  • Example 7 Preparation of 4-hydroxyprenyl phenyl sulfoxide and sulfone To a solution of 4-hydroxyprenyl phenyl sulfide (97 mg, 0.5 mmol) dissolved in methanol (2.5 ml), was added LiNbMoO ⁇ (7.3 mg, 0.05 mmol) as a catalyst, and then 34%) aqueous hydrogen peroxide solution (50 mg, 0.50 mmol) was slowly added thereto. After stirring at 0°C for 1 hour, the reaction mixture was worked up according to the same procedure of Example 1. to give pure 4-hydroxyprenyl phenyl sulfoxide (79 mg, 0.38 mmol, yield: 75%).
  • 4-hydroxyprenyl phenyl sulfone was prepared as follows: To a solution of 4-hydroxyprenyl phenyl sulfide (0.60 g, 3.2 mmol) dissolved in methanol (15 ml), was added LiNbMo0 6 (46 mg, 0.20 mmol) as a catalyst, and then 30%) aqueous hydrogen peroxide solution (0.96 g, 9.5 mmol) was slowly added thereto.
  • benzyl phenyl sulfone was prepared as follows: To a solution of benzyl phenyl sulfide (2.00 g, 10.0 mmol) dissolved in methanol (50 ml), was added LiNbMo0 6 (0.15 mg, 0.50 mmol) as a catalyst, and then 30%) aqueous hydrogen peroxide solution (3.40 g, 30.0 mmol) was slowly added thereto. After stirring at room temperature for 4 hours, the reaction mixture was worked up according to the same procedure of Example 1 , to give the objective sulfone (2.27 g, 9.8 mmol, yield: 98%).
  • the NMR data of the obtained benzyl phenyl sulfone are shown below:
  • Example 9 Preparation of diprenyl sulfoxide and sulfone To a solution of diprenyl sulfide (85 mg, 0.50 mmol) dissolved in methanol
  • LiNbMo0 6 (7.3 mg, 0.05 mmol) as a catalyst, and then 34% aqueous hydrogen peroxide solution (50 mg, 0.50 mmol) was slowly added thereto.
  • diprenyl sulfone was prepared as follows: To a solution of diprenyl sulfide (0.60 g. 3.5 mmol) dissolved in methanol (18 ml), was added LiNbMo0 6 (51 mg, 0.20 mmol) as a catalyst, and then 30%> aqueous hydrogen peroxide solution (1.00 g, 10.1 mmol) was slowly added thereto. After stirring at room temperature for 4 hours, the reaction mixture was worked up according to the same procedure of Example 1, to give the objective sulfone (0.43 g, 2.1 mmol. yield: 71%o).
  • the NMR data of the obtained diprenyl sulfone are shown below:
  • digeranyl sulfone was prepared as follows: To a solution of digeranyl sulfide (3.57 g, 1 1.7 mmol) dissolved in methanol (40 ml), was added LiNbMo0 6 (0.17 g, 0.60 mmol) as a catalyst, and then 30%> aqueous hydrogen peroxide solution (3.96 g, 35.0 mmol) was slowly added thereto. After stirring at room temperature for 4 hours, the reaction mixture was worked up according to the same procedure of Example 1, to give the objective sulfone (2.84 g, 8.4 mmol, yield: 72%).
  • the NMR data of the obtained digeranyl sulfone are shown below:
  • the present invention provides a process for selectively preparing a sulfoxide or a sulfone compound from the corresponding sulfide by the use of LiNbMo0 6 -H 2 0 2 oxidant system having both reactivity and selectivity, under the condition of controlling the quantitative amount of the oxidant.
  • the process according to the present invention is economically advantageous as the process employs cheap hydrogen peroxide as the quantitative oxidant, and easily carried out as it employs LiNbMo0 6 as a composite metal oxide catalyst which is ready to handle with good stability at room temperature.
  • the process is carried out in high yield under mild condition, and the reaction product can be easily worked-up.
  • the process according to the present invention is very efficient on the oxidation of an allylic sulfide comprising double bond(s) with high electron density to a sulfone which was very difficult to be obtained by means of conventional processes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé d"oxydation sélective d"un sulfure au moyen d"un système constitué de niobate de molibdénate de lithium (LiNbMoO6) et de peroxyde d"hydrogène, d"où l"obtention d"un composé de sulfoxyde ou de sulfone correspondant en quelques heures dans une condition de régulation de la quantité de peroxyde d"oxygène et en présence d"un solvant d"alcool. Le procédé d"oxydation de sulfure de la présente invention présente un avantage économique en vue d"une application industrielle ainsi qu"à l"échelle du laboratoire étant donné qu"il est mis en oeuvre dans des conditions douces, qu"il implique un processus simple et que les réactifs sont faciles à manipuler. Plus particulièrement, selon la présente invention, des sulfures allyliques dotés d"une ou de plusieurs doubles liaisons de densité électronique élevée liée à une substitution d"alkyle ou à une conjugaison étendue, et aptes à être attaqués par des oxydants électrophiles, peuvent être soumis à une oxydation sélective permettant d"obtenir des sulfones ou des sulfoxydes sans oxydation desdites doubles liaisons.
PCT/KR2001/000252 2000-02-23 2001-02-22 Oxydation selective de sulfures au moyen d"un systeme oxydant constitue de niobate de molibdenate de lithium et de peroxyde d"hydrogene WO2001062719A1 (fr)

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AU2001236161A AU2001236161A1 (en) 2000-02-23 2001-02-22 Selective oxidation of sulfides by the use of an oxidant system consisting of lithium molibdenate niobate and hydrogen peroxide

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KR2000-9701 2000-02-23
KR20000009701 2000-02-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102086167A (zh) * 2010-12-09 2011-06-08 济南大学 一种乙磺酰基乙腈的制备方法
RU2668810C1 (ru) * 2017-08-07 2018-10-08 Федеральное Государственное Бюджетное Учреждение Науки Институт Химии Коми Научного Центра Уральского Отделения Российской Академии Наук Способ получения нефтяных сульфоксидов
EP3421442A1 (fr) 2017-06-28 2019-01-02 Construction Research & Technology GmbH Dispersant pour particules inorganiques

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025565A (en) * 1972-02-22 1977-05-24 Asahi Glass Co., Ltd. Process for preparing unsaturated aldehyde having three to four carbon atoms
EP0124845A1 (fr) * 1983-05-10 1984-11-14 I.M.F. Industria Macchine Faenza S.P.A. Dispositif de positionnement d'une unité d'usinage par rapport à une pièce de travail, en particulier pour des lignes de transfer
WO1998013329A1 (fr) * 1996-09-24 1998-04-02 E.I. Du Pont De Nemours And Company Catalyseurs d'oxydation a base de molybdene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025565A (en) * 1972-02-22 1977-05-24 Asahi Glass Co., Ltd. Process for preparing unsaturated aldehyde having three to four carbon atoms
EP0124845A1 (fr) * 1983-05-10 1984-11-14 I.M.F. Industria Macchine Faenza S.P.A. Dispositif de positionnement d'une unité d'usinage par rapport à une pièce de travail, en particulier pour des lignes de transfer
WO1998013329A1 (fr) * 1996-09-24 1998-04-02 E.I. Du Pont De Nemours And Company Catalyseurs d'oxydation a base de molybdene

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A.V. RAMASWAMY AND S. SILVASANKER: "Selective oxidation reactions over titanium and vanadium metallosilicate molecular sieves", CATALYSIS LETTERS, vol. 22, no. 3, 1993, pages 239 - 249 *
CAROLE DUBOC-TOIA ET AL.: "Enantioselective sufoxidation as a prove for a metal-based mechanism in H2O2-dependent oxidation catalyzed by a Diiron complex", INORGANIC CHEMISTRY, vol. 38, no. 6, 1999, pages 1261 - 1268 *
TAKAHIRO IWAHAMA ET AL.: "Selective oxidation of sulfides to sulfoxides with molecular oxygen catalyzed by N-hydroxyphthalimide(NHPI) in the presence of alcohols", TETRAHEDRON LETTERS, vol. 39, no. 49, 1998, pages 9059 - 9062, XP004141002, DOI: doi:10.1016/S0040-4039(98)02054-1 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102086167A (zh) * 2010-12-09 2011-06-08 济南大学 一种乙磺酰基乙腈的制备方法
CN102086167B (zh) * 2010-12-09 2013-05-08 济南大学 一种乙磺酰基乙腈的制备方法
EP3421442A1 (fr) 2017-06-28 2019-01-02 Construction Research & Technology GmbH Dispersant pour particules inorganiques
RU2668810C1 (ru) * 2017-08-07 2018-10-08 Федеральное Государственное Бюджетное Учреждение Науки Институт Химии Коми Научного Центра Уральского Отделения Российской Академии Наук Способ получения нефтяных сульфоксидов

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