WO2009014431A1 - Production sélective de sulfoxydes - Google Patents

Production sélective de sulfoxydes Download PDF

Info

Publication number
WO2009014431A1
WO2009014431A1 PCT/NL2008/050444 NL2008050444W WO2009014431A1 WO 2009014431 A1 WO2009014431 A1 WO 2009014431A1 NL 2008050444 W NL2008050444 W NL 2008050444W WO 2009014431 A1 WO2009014431 A1 WO 2009014431A1
Authority
WO
WIPO (PCT)
Prior art keywords
ozonide
thio
ozone
olefin
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL2008/050444
Other languages
English (en)
Inventor
Markus Nobis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dishman Carbogen Amcis Ltd
Pluim Henk
Original Assignee
Dishman Pharmaceuticals and Chemicals Ltd
Pluim Henk
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dishman Pharmaceuticals and Chemicals Ltd, Pluim Henk filed Critical Dishman Pharmaceuticals and Chemicals Ltd
Publication of WO2009014431A1 publication Critical patent/WO2009014431A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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 invention pertains to a selective process for producing sulphoxides from thioethers.
  • Ozonolysis the process of forming ozonide from the reaction of an olefin with ozone, is well-known in the art.
  • ozonide has presently found use in the reduction of olefins, converting unsaturated bonds to carbonyl groups.
  • Ozonide has never been mentioned as an oxidizing agent, let alone a selective one. The benefits from its controlled manufacture and subsequent use in sulphoxide production are yet unknown.
  • ozonide makes a complete and selective conversion of thio-ether precursors into sulphoxides industrially feasible, provided that the total amount of ozonide is at least identical but preferably exceeds that of the sulphide moieties in the thio-ether precursor.
  • the end-product is free from any sulphones.
  • the invention thus pertains to a process for producing a sulphoxide compound, comprising oxidizing a thioether compound with an ozonide formed from a olefin and ozone, to obtain the corresponding sulphoxide compound, provided that the olefin is not ethene. Since it is unpractical to produce an ozonide from ethene and ozone, its use does not part of the invention.
  • the process of the present invention may be characterized as being "sulphone- free", meaning that no detectable amount of sulphone moieties is formed throughout the reaction process.
  • ozonide has its meaning as recognized in the art, i.e. the reaction product formed from olefin and ozone.
  • the ozonide may schematically be represented by formula (I)
  • Rl, R2, R3, R4 represent, independently, hydrogen or an organic component, and/or wherein two or more of Rl, R2, R3, R4 maybe covalently interconnected, provided that Rl -4 are not hydrogen simultaneously, thus excluding ethene.
  • the ozonide is sometimes alternatively drawn up as:
  • Rl - R4 having the above meaning.
  • the invention is not regarded being tied by the exact structural representation of the ozonide.
  • ozonide is mentioned in the context of the invention, it encompasses either of the above schematic representations, provided that the ozonide is formed from reacting an olefin with ozone, in the art referred to as "ozono lysis".
  • the molar ratio of the ozonide to the thio-ether compound is preferably at least 1, in order to complete the oxidation into sulphoxide. The molar ratio is calculated on the basis of the amount of thio-ether functionalities or sulphide moieties present in the precursor.
  • the ratio is in the range of 1.1- 4, preferably 1.2 - 3.
  • high amounts of ozonide do not result in over- oxidation.
  • the step of producing sulphoxides is free from ozone, i.e. contact between ozone and the sulphide groups is avoided.
  • thio-ether oxidation may be characterized as being "ozone- free", i.e. wherein ozone is not deliberately added and not present in detectable amounts. Thereto, ozonide may be produced separately.
  • Ozonide may be supplied to the thio-ether precursor batchwise or continuously, e.g. by dropwise addition. However, it is stressed once more that a continuous and controlled supply of ozonide is redundant from the perspective of avoiding over- oxidation.
  • Ozonolysis is a well-documented reaction route, albeit for a different intended use, and the skilled person will be readily able to determine the desired reaction conditions with general knowledge from the prior art. Nevertheless, few details are given here below.
  • Ozone may be produced using pure oxygen or mixtures of oxygen and inert gases in varying volumetric ratios to oxygen, preferably between 1 and 80 vol.%.
  • the gaseous ozone is then added to the reaction mixture containing the olefin.
  • the ozone concentration in the gas supplied to the reaction mixture lies preferably within the range of 1 to 12 % by weight in relation to the total gas used. Especially preferred are ozone concentrations in the range of 4 to 8 % by weight.
  • Ozone can be introduced to the reaction mixture for olefin conversion in a molar range of 1 to 5, or preferably in the range of 1 to 3 and most preferably in the range of 1.1 to 2 molar equivalents, calculated on the molar amount of olefin. Under these conditions any undesired sideproducts of ozonolysis are minimized.
  • the olefin-containing reaction mixture preferably contains 2 to 50 % by weight, more preferably 4 - 25 wt%, most preferably 7.5 to 10 wt% of olefin, based on the total weight of the reaction mixture.
  • oxidation-stable aromatic or non-aromatic solvents For the production of the ozonides, it is preferred to use oxidation-stable aromatic or non-aromatic solvents.
  • the solvent must be suitable for use in an ozonolysis.
  • Preferred solvents include substituted or non-substituted aromatic hydrocarbons or solvents which possess oxygen in the form of carbonyl, ether or alcohol functions.
  • Halogenated aromatic and non-aromatic solvents have proved suitable for performing the reaction.
  • Solvents with other oxidizable hetero-atoms are likewise suitable, as a result of the high selectivity of the process. Because of the solubility of the reaction participants in toluene or alcohols, or mixtures of them, they are particularly preferred.
  • Ozonolysis is preferably performed at a temperature of -78°C to +30 0 C, in particular at -30 0 C to +10 0 C, and most preferably at -10 0 C to 0 0 C. Under these conditions secondary reactions of the ozonolysis and a potential hazard caused by exceeding the ignition temperature of one the reaction components can be avoided.
  • the final ozonlysis reaction mixture, containing the ozonide thus-formed, may be applied in the subsequent oxidation process without any intermediate isolation or purification steps. In principle, it is possible to perform the subsequent oxidation after ozonlysis as a "one-pot synthesis", provided that the ozone throughput is conveniently stopped before introducing the thio-ether compound, i.e.
  • the structure of the ozonide of the present invention is determined by the conformation of the olefin bonding used for the synthesis.
  • Rl, R2, R3 and R4 represent, independently, hydrogen or an organic component, independently (with preferably no more than 100 C-atoms), preferably a substituted component selected from the group comprising alkyl, heteroalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, cycloalkenyl, cycloalkenylalkyl, alkinyl, cycloalkylalkinyl, alkoxy, cycloalkoxy, cycloalkylalkoxy, aryl, heteroaryl, arylalkyl, cycloalkylaryl, cycloalkenylaryl, cycloalkylheteroaryl, heterocycloalkylaryl, heterocycloalkenylaryl, heterocycloalkenylheteroaryl and heteroarylalkyl, and/or two or more of Rl, R2, R3, R4 are covalently interconnected, provided that the olefin is not e
  • Rl - R4 are aromatically or non-aromatically substituted, the substituent(s) is/are preferably selected from the group consisting of:
  • Ci-Cs-Alkyl preferably Methyl, Ethyl, n-Propyl, iso -Propyl, n-Butyl, iso- Butyl, tert- Butyl,
  • Cyclopropyl preferably Cyclopropyl, Cyclopentyl, Cyclohexyl, Cyclooctyl, Cyclododecyl, Cyclopentadecyl, Cyclohexadecyl,
  • Ci-C 8 -Perfiuoralkyl preferably Trifiuormethyl, Nonafluorbutyl,
  • Ci -Cs- Alkoxy preferably Methoxy, Ethoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, tert.- Butoxy, - C3-Ci2-Cycloalkoxy, preferably C ⁇ -Cycloalkoxy, Cs-Cycloalkoxy, C ⁇ -Cycloalkoxy, C ⁇ -Cycloalkoxy, Ci2-Cycloalkoxy, Cis-Cycloalkoxy, Ci6-Cycloalkoxy,
  • Ci-C 4 -Carboxy preferably CO 2 Me, CO 2 Et, CO 2 iso-Pr, C0 2 tert.-Bu,
  • Ci-CzrAcyloxy preferably Acetyloxy, - halogen, preferably F or Cl,
  • oxidizing agents are ozonides are those given by formula (I), in which Rl, R2, R3, R4 independently represent a substituted component selected from the group consisting of C 3 -C 25 -ArVl, C2-C2 5 -Heteroaryl, C 4 -C 25 -Arylalkyl, C 8 -C 25 -Cycloalkylaryl, Cs-C 25 -Cycloalkenylaryl, C 5 -C 25 -Cycloalkylheteroaryl, C 8 -C 25 -Heterocycloalkylaryl, Cs-C 25 -Heterocycloalkenylaryl, Cs-C 25 -
  • Heterocycloalkenylheteroaryl and C 3 -C 25 -Heteroarylalkyl provided that the ozonide structure lacks a symmetry axis, i.e. if not all of R1-R4 are the same.
  • the most preferred ozonides are those according to formula (I), in which Rl, R2, R3, R4 independently represent substituted groups selected from the group consisting of C 6 -C 2 o-Aryl, C 3 -C 20 -Heteroaryl, C 7 -C 20 -Arylalkyl, C 8 -C 2 o-Cycloalkylaryl, C 8 -C 20 - Cycloalkenylaryl, C 6 -C 2 o-Cycloalkylheteroaryl, C 8 -C 2 o-Heterocycloalkylaryl, Cs-C 20 - Heterocycloalkenylaryl, Cs-C 2 o-Heterocycloalkenylheteroaryl and C 4 -C 20 - Heteroarylalkyl, in particular those selected from the group consisting of C 6 -C 20 -Aryl, C 3 -C 20 -Heteroaryl, Cs-C 20 -Cyclo
  • C 6 -C 20 -Aryl from the group consisting of Phenyl, A- Methoxyphenyl, 2,4-Dimethoxyphenyl, 4-Methylyphenyl, 2,4-Dimethylphenyl, 3,5- Dimethylphenyl, 2-Tert.-butylphenyl, 4-Tert.-butylphenyl, 2,6-Di-tert.-butylphenyl, A- CF 3 -phenyl, 2,4-Di-CF 3 -phenyl, 1-Naphthyl, 2-Naphthyl, 9-Anthacenyl, 9- Phenanthrenyl.
  • C 3 -C 20 -Heteroaryl preferably comprise 2- Furfuryl, 3-Furfuryl, Imidazolyl.
  • Cs-C 20 -Cycloalkylaryl preferably comprise Indanyl, Fluorenyl.
  • Cs-C 20 -Cycloalkenylaryl is preferably Indenyl.
  • Especially preferred Cs-C 2 o-Heterocycloalkenylaryl is N-Ci-Ci 6 -Alkyl- or N- C 1 - Cs-Acyl-Indolyl.
  • C 6 -C 2 o-Heterocycloalkylaryl is N-Ci-Ci ⁇ -Alkyl- or N-C 1 -C 8 - Acyl-Indolinyl.
  • Reaction during subsequent thioether oxidation is preferably in the range of -78 0 C to +70 0 C, in particular -30 0 C to +80 0 C and most preferably 20 0 C to 60 0 C. At these conditions fast and selective conversion of the thio -ether can be assured.
  • the reaction temperature is restricted to the mutual overlap between the aforementioned temperature trajects.
  • both reaction steps may perform optimally at different temperature conditions and ozone may hinder the selectivity of the reaction process, it is preferred to perform both steps separately, i.e. performing thio-ether oxidation after ozonolysis.
  • selectivity of the process is not affected by the order in which the components of the oxidation are mixed with one another. However, for sake of convenience, is preferred to add the oxidizing agent to the thio-ether precursor.
  • the thio-ether precursor is not particularly restricted to a certain group of thio -ethers.
  • the ozonide has shown to be a successful tool in selectively converting each and everyone of the sulphide moieties investigated.
  • Applicant's interest particularly concern those thio -ethers known as API precursors, such as lanzoprazole, pantoprazole, omeprazole and rabeprazole.
  • the invention particularly relates to the formation of a sulphoxide compound which is represented by formula (II) in which
  • RaI, Ra2, Ra3, RbI, Rb2 and Rb3 each represent, independently, H or an organic component (with preferably no more than 100 C-atoms), and preferably a substituted component selected from the group comprising alkyl, heteroalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, cycloalkenyl, cycloalkenylalkyl, alkinyl, cycloalkylalkinyl, alkoxy, cycloalkoxy, cycloalkylalkoxy, aryl, heteroaryl, arylalkyl, cycloalkylaryl, cycloalkenylaryl, cycloalkylheteroaryl, heterocycloalkylaryl, heterocycloalkenylaryl, heterocycloalkenylheteroaryl and heteroarylalkyl, in which two or all of Ra, and/or two or all of Rb may independently be covalently linked; and xl,
  • Ra and/or Rb are aromatic, these may be substituted with: Hydroxy;
  • Ci -Cs- Alkyl preferably Methyl, Ethyl, n-Propyl, iso -Propyl, n-Butyl, iso- Butyl, tert- Butyl;
  • C 3 -Ci 8 -Cycloalkyl preferably Cyclopropyl, Cyclopentyl, Cyclohexyl, Cyclooctyl, Cyclododecyl, Cyclopentadecyl, Cyclohexadecyl; C 2 -C 8 -Alkinyl, preferably Ethinyl, Propinyl; Ci-C 8 -Perfluoralkyl, preferably Trifluormethyl, Nonafluorbutyl; Ci-Cs-Alkoxy, preferably Methoxy, Ethoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, tert.- Butoxy;
  • Ci-C4-Acyl preferably Acetyl
  • Ci-C 4 -Carboxy preferably CO 2 Me, CO 2 Et, CO 2 iso-Pr, C0 2 tert.-Bu; Ci-C4-Acyloxy, preferably Acetyloxy; Halogenid, preferably F or Cl; Sii-Siio-Silyl; and/or Sii-Si ⁇ o-Siloxy or Polysiloxy.
  • Ra and Rb may independently be selected from the group consisting of C 3 - C 25 -Aryl, C 2 -C 25 -Heteroaryl, C 4 -C 25 -Arylalkyl, C 8 -C 25 -Cycloalkylaryl, C 8 -C 25 - Cycloalkenylaryl, C 5 -C 25 -Cycloalkylheteroaryl, C 8 -C 25 -Heterocycloalkylaryl, C 8 - C 25 -Heterocycloalkenylaryl, C 8 -C 25 -Heterocycloalkenylheteroaryl and C 3 -C 25 - Heteroarylalkyl.
  • Ra and Rb may independently be selected from the group consisting of C6-C 2 o-Aryl, C 3 -C 2 o-Heteroaryl, C7-C 2 o-Arylalkyl, C 8 -C 2 O- Cycloalkylaryl, C 8 -C 2 o-Cycloalkenylaryl, C 6 -C 2 o-Cycloalkylheteroaryl, C 8 -C 2O - Heterocycloalkylaryl, C 8 -C 2 o-Heterocycloalkenylaryl, C 8 -C 2 O- Heterocycloalkenylheteroaryl and C 4 -C 2 o-Heteroarylalkyl.
  • - C 6 -C 2 o-Aryl is preferably selected from Phenyl, 4-Methoxyphenyl, 2,4-
  • - C 8 -C 2 o-Cycloalkylaryl is preferably Indanyl, Fluorenyl;
  • C 8 -C 2 o-Cycloalkenylaryl is preferably Indenyl;
  • C 8 -C 2 o-Heterocycloalkenylaryl is preferably N-Ci-Ci 6 -Alkyl- or N- C i-Cs- Acyl-Indolyl;
  • - C6-C2o-Heterocycloalkylaryl is preferably N-C 1 -C 16 -AIlCyI- or N-C 1 -C 8 -ACyI-
  • Ra and Rb contain oxidizable hetero- atoms, as for example nitrogen or phosphorous, it is not necessary for the conversion of the thio -ether to further protect them with an oxidation agent.
  • the invention further pertains to the use of an ozonide as described above as an oxidizing agent, in particular to selectively convert sulphide groups.
  • trans-stilbene (0.028 mol) suspended in 50 ml methanol at -20 0 C was supplied with 1.2 molar equivalents of ozone. A trans-stilbene-ozonide was produced, which was present as a clear, weakly yellow solution in methanol.
  • Example 2 Synthesis of diphenylsulfoxide from Diphenylsulfide A trans-stilbene ozonide was prepared using the recipe of example 1.
  • a cold solution containig 0.037 mol of the freshly produced ozonide was added drop-wise to a solution of diphenylsulfide (5.7g/0.031 mol) in 100 ml methanol at a reaction temperature of 50 0 C. Conversion was completed after 2 hours, resulting in diphenylsulfoxide. The selectivity was 100 %, as determined with GC-MS.
  • Example 3 Synthesis of Methylphenylsulfoxide from Thioanisole A trans-stilbene ozonide was prepared using the recipe of example 1.
  • Example 4 Production of Benzylmethylsulfoxide Example 3 was repeated, with the exception that the thio -ether in step b) was benzylmethylsulfide (4.3g/0.031 mol), and 0.062 mol trans-stilbene-ozonide was used. Benzylmethylsulfoxide was thus prepared, with a selectivity of 100 %.
  • Trans-stilbene ozonide was prepared following the recipe of example 1, in an amount of 0.031 mol.
  • the thus-prepared ozonide was added drop-wise over 0.5h to a boiling solution of sulfide (0.031 mol) in 100 ml of methanol.
  • the reaction solution is boiled for 3 hours under reflux conditions.
  • the experiment was performed for a number of sulfides, generally represented by formula III. After 3 hours, the reaction mixtures were analyzed for conversion rate. The results are shown in table 1. In all cases, sulfoxide selectivity was 100%.
  • the solution was used directly for the oxidation of the sulfides represented by formula III. Thereto, the ozonide was added dropwise over 0.5h to the boiling solution of the sulfide (0.20 mol) in 200 ml methanol. The reaction solution was refluxed for 3 hours. After 3 hours, the reaction mixtures were analyzed for conversion rate. The results are shown in table 2. In all cases, sulfoxide selectivity was 100%.

Landscapes

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

Abstract

L'invention porte sur un procédé de fabrication d'un composé sulfoxyde comprenant l'oxydation d'un composé thioéther par un ozonide formé à partir d'une oléfine et d'ozone, afin d'obtenir un composé sulfoxyde correspondant, à la condition que l'oléfine ne soit pas de l'éthène. L'ozonide convertit les composés thioéther de façon sélective à la différence de ses contreparties d'oxydation connues dans la technique. L'ozonide plus doux ne nécessite pas de manipulation de la quantité stoechiométrique d'agent oxydant disponible pendant la réaction, afin d'empêcher la formation de sulfones.
PCT/NL2008/050444 2007-07-23 2008-07-02 Production sélective de sulfoxydes Ceased WO2009014431A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07112926.6 2007-07-23
EP07112926 2007-07-23

Publications (1)

Publication Number Publication Date
WO2009014431A1 true WO2009014431A1 (fr) 2009-01-29

Family

ID=38895620

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2008/050444 Ceased WO2009014431A1 (fr) 2007-07-23 2008-07-02 Production sélective de sulfoxydes

Country Status (1)

Country Link
WO (1) WO2009014431A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2722324A4 (fr) * 2011-06-17 2014-11-12 Unimatec Co Ltd Procédé pour produire de l'hexafluoroacétone ou un hydrate de celle-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637768A (en) * 1969-03-18 1972-01-25 Texaco Development Corp Epoxidation of olefin with an oxolane
US6437189B1 (en) * 1997-12-12 2002-08-20 Bayer Corporation Synthesis of sulfoxides via selective oxidation of sulfides with a perborate or a percarbonate
WO2006131040A1 (fr) * 2005-06-07 2006-12-14 The Xinjiang Technical Institute Of Physics & Chemistry Chinese Academy Of Sciences Procede de preparation de l'acide glyoxalique par oxydation du glyoxal avec l'ozonide de l'acide maleique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637768A (en) * 1969-03-18 1972-01-25 Texaco Development Corp Epoxidation of olefin with an oxolane
US6437189B1 (en) * 1997-12-12 2002-08-20 Bayer Corporation Synthesis of sulfoxides via selective oxidation of sulfides with a perborate or a percarbonate
WO2006131040A1 (fr) * 2005-06-07 2006-12-14 The Xinjiang Technical Institute Of Physics & Chemistry Chinese Academy Of Sciences Procede de preparation de l'acide glyoxalique par oxydation du glyoxal avec l'ozonide de l'acide maleique

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
AKIRA MATSUURA ET AL: "Pd(II)-Mediated Oxidatin of Olefins Using the Transannular Ozonides of 9-tert-Butylanthracenes as an Oxygen Atom Source", J. ORG. CHEM., vol. 50, 1985, pages 5002 - 5004, XP002464357 *
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002464347, retrieved from XFIRE Database accession no. 1840511 *
J. ORG. CHEM., vol. 49, no. 23, 1984, pages 4465 - 4470 *
SHERESHOVETS V V: "OXIDATION OF SULFIDES TO SULFOXIDES BY OPTICALLY ACTIVE PHOSPHITE OZONIDES", BULLETIN OF THE ACADEMY OF SCIENCES OF THE USSR. DIVISION OF CHEMICAL SCIENCE, CONSULTANTS BUREAU. NEW YORK, US, vol. 39, no. 9, 1 September 1990 (1990-09-01), pages 1943 - 1945, XP000219211 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2722324A4 (fr) * 2011-06-17 2014-11-12 Unimatec Co Ltd Procédé pour produire de l'hexafluoroacétone ou un hydrate de celle-ci

Similar Documents

Publication Publication Date Title
Yuan et al. Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer
Azizi et al. Intermolecular difunctionalization of alkenes: synthesis of β-hydroxy sulfides
Zhu et al. Methylrhenium trioxide as a catalyst for oxidations with molecular oxygen and for oxygen transfer
US20050272966A1 (en) Process for converting methane into ethane
RU2186767C2 (ru) Способ получения гидропероксидов
Hitce et al. Flash-metathesis for the coupling of sustainable (poly) hydroxyl β-methylstyrenes from essential oils
Gómez et al. Green and chemoselective oxidation of sulfides with sodium perborate and sodium percarbonate: nucleophilic and electrophilic character of the oxidation system
JP2008517048A (ja) 有機化合物の選択的酸化
MY134799A (en) Catalyst comprising cyclic acylurea compound and process for producing organic compounds using the catalyst
DE60208372D1 (de) Verfahren zur bereitung von organosilikonverbindungen die schwefel enthalten
IN2010DN07192A (fr)
WO2009014431A1 (fr) Production sélective de sulfoxydes
GB2136422A (en) Synthesis of nitrones and nitrone addition products from secondary amines
WO2004018529A3 (fr) Catalyseur de ziegler modifie, procede pour sa preparation et procede pour preparer une poly-1-olefine en sa presence
JPH042587B2 (fr)
JPH02272A (ja) アルキルチオエチルアミン塩類の製造プロセス
WO2002094771A1 (fr) Procede de fabrication d'un compose contenant du soufre
US20040063932A1 (en) Stable free nitroxyl radicals as oxidation catalysts and process for oxidation
Bushkov et al. Ti-catalyzed heterometathetical condensation of N-sulfinylamines into sulfurdiimines
Takeuchi et al. One-step arylthiolation to aromatic compounds by disulfide radical cations generated from oxidation of diaryl disulfides with aluminium chloride
JPS60178829A (ja) 含フツ素芳香族誘導体の製造法
JP2006506468A (ja) カルボニル化合物の製造に関する触媒的方法
US6063950A (en) Process for the preparation of titanocene dichloride
JPS63287789A (ja) モリプデンの炭化水素置換ジチオカルバメ−トの製造法
EP0365382A1 (fr) Procédé d'aminocarbonylation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08766867

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08766867

Country of ref document: EP

Kind code of ref document: A1