EP2616475A1 - Complexe de molybdène acétylide dioxo organométallique et procédé de préparation associé - Google Patents

Complexe de molybdène acétylide dioxo organométallique et procédé de préparation associé

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Publication number
EP2616475A1
EP2616475A1 EP11776595.8A EP11776595A EP2616475A1 EP 2616475 A1 EP2616475 A1 EP 2616475A1 EP 11776595 A EP11776595 A EP 11776595A EP 2616475 A1 EP2616475 A1 EP 2616475A1
Authority
EP
European Patent Office
Prior art keywords
complex
dioxo
molybdenum
acetylide
formula
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.)
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Application number
EP11776595.8A
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German (de)
English (en)
Inventor
Shubhangi Bhalchandra Umbarkar
Mohan Keraba Dongare
Ankush Biradar
Vaibhav Ravindrakumar Acham
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.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
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 Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Priority claimed from PCT/IN2011/000627 external-priority patent/WO2012035555A1/fr
Publication of EP2616475A1 publication Critical patent/EP2616475A1/fr
Withdrawn legal-status Critical Current

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Definitions

  • Present invention relates to organometallic molybdenum acetylide dioxo complex of formula (ri 5 -C 5 H 5 )Mo0 2 (-C ⁇ CPh).
  • the present invention relates to process using molybdenum oxide precursor for the preparation of organometallic molybdenum acetylide dioxo complex of formula ( ⁇ 5 - C s Hs)lvlo02(-CsCPh).
  • Present invention further relates, to a process for the synthesis of the complex useful as a catalyst for various oxidation reactions.
  • transition metal dioxo organometallic complexes are prepared using corresponding transition metal carbonyl complexes involving multistep synthesis process as well as tedious work up procedure. These transition metal complexes are converted to corresponding dioxo /oxo-peroxo by treating with various oxidants like hydrogen peroxide, t- butyl hydrogen peroxide or cumyl hydrogen peroxide.
  • Pentamethyl cyclopentadienyl tungsten acetylide dioxo and oxo-peroxo complexes have been prepared by pentamethyl cyclopentadienyl tungsten tricorbonyl acetylide complex by treating with sulfuric acid and Hydrogen peroxide in toluene at room temperature for 24 hr.
  • This process for the preparation of cyclopentadienyl transition metal dioxo organometallic complexes is cumbersome and results in the release of carbon monoxide as a by-product making it environmentally unacceptable. Further, the process is not viable for commercial applications because of use of costly metal carbonyls as starting material.
  • Main objective of the present invention is to provide organometallic molybdenum acetylide dioxo complex of formula (Ti 5 -C 5 H 5 )Mo0 2 (-CsCPh). US 211
  • Another objective of the present invention is to provide process using molybdenum oxide precursor for the preparation of organometallic molybdenum acetylide dioxo complex of formula (Ti 5 -C 5 H 5 )lv1o0 2 ⁇ -G ⁇ CPh) which is useful as a catalyst for various oxidation reactions.
  • present invention provides organometallic molybdenum acetylide dioxo complex of formula (ri 5 -C 5 H 5 )Mo0 2 (-OCPh ⁇ .
  • said organometallic molybdenum acetylide dioxo complex is useful as a catalyst for the oxidation of olefins, alcohols, anilines, sulfides .and alkanes.
  • said complex is recyclable.
  • process for preparation of organometallic molybdenum acetylide dioxo complex of formula (rj 5 -CsH 5 ) o0 2 ⁇ -C ⁇ CPh) comprising the steps of:
  • catalytically active species (TI 5 -C 5 H 5 ) MoO(0 2 )(-C ⁇ CPh) of the said organometallic molybdenum dioxo complex (TI S -C 5 H 5 ) MO0 2 (- CsCPh) formed after reacting with hydrogen peroxide is water soluble.
  • yield of molybdenum acetylide dioxo complex of formula (n. 5 -C 3 H 5 )Mo0 2 (-C3CPh) is in the range of 40 to 85%.
  • Figure 1 is IR spectrum of the ( 5 -C 5 H 5 )Mo0 2 (-CsCPh) catalyst.
  • the present invention provides a simple process for the preparation of organometallic molybdenum dioxo complex ⁇ 5 -C 5 H 5 )Mo0 2 (-CsCPh) as a catalyst starting from simple precursor like molybdenum trioxide, M0O3 instead of molybdenum hexacarbonyl as disclosed in prior art.
  • the process comprises:
  • step b Adding dimethylsulphoxide or N, N Dimethyl formamide to dihalo dioxo molybdenum of step a to form greenish adduct, Mo0 2 X 2 .2DMSO or Mo0 2 X 2 .2DMF respectively;
  • Such organometallic molybdenum dioxo complex finds use as catalysts for various reactions.
  • the catalyst is active for oxidation reactions such as oxidation of cyclohexene to cis diol similar to Sharpless catalyst.
  • the catalyst is active for oxidation reactions such as oxidation of alcohols, anilines, olefins, sulfides and such like.
  • the catalyst has shown activity for oxidation reactions and even though it is homogeneous catalyst, being water soluble it can be recovered after the oxidation reaction by dissolving in water and separating it from organic phase for recovery and recycle, as exemplified herein with reference to example 12.
  • the complex of the invention becomes water soluble on dissolution after reacting with hydrogen peroxide and is recovered from the oxidation reactions from the aqueous layer.
  • Molybdenum trioxide (Mo0 3 , 1.44 g, 10 mmol) was treated with cone, aqueous hydrochloric acid (7 ml, 35%) at 60°C for 2 h to form aqua complex of dichloro dioxo molybdenum (MoO 2 CI 2 .2H 2 0). In the same reaction mixture was added 2.5 ml of dimethylsulphoxide (DMSO) to form the greenish adduct Mo0 2 CI 2 .2DMSO.
  • DMSO dimethylsulphoxide
  • Mo0 2 CI 2 .2DMSO was treated with sodium LLS 211 cyclopentadiene (CpNa, synthesized by reaction of sodium (253 mg, 11 mmol) with freshly cracked cyclopentadiene (743 mg, 11 mmol) in THF) and stirred for 3 h to form cyclopentadiene dioxomolybdenum chloride complex (Cp o0 2 Cl).
  • Cp o0 2 Cl cyclopentadiene dioxomolybdenum chloride complex
  • Another round bottom flask was charged with phenyl acetylene ((PhC ⁇ CH) 1.10 g, 11 mmol) using copper (I) iodide (Cul, 5 mg) and diethyl amine (40 ml) and stirred for 30 min. This phenyl acetylene mixture was added to the first flask and stirred for 3 h at 30°C to form CpMo0 2 (-C ⁇ CP
  • Molybdenum trioxide (M0O 3 , 1.44gm, 10 mmol) was reacted with cone, aqueous hydrochloric (7ml, 35%) acid at 60°C for 2 h to form aqua complex of dichloro dioxo molybdenum (Mo0 2 CI 2 .2H 2 0).
  • DMF N, N-dimethyl formamide
  • Mo0 2 CI 2 .2DMF was treated with sodium cyclopentadiene (CpNa, synthesized by reaction of sodium (253 mg, 11 mmol) with freshly cracked cyclopentadiene (743 mg, 11 mmol) in THF) and stirred for 3 h to form cyclopentadiene dioxomolybdenum chloride complex (CpMo0 2 CI).
  • Molybdenum trioxide (Mo0 3 ⁇ 1.44gm, 10 mmol) was reacted with cone, aqueous hydrochloric (7 ml, 35%) acid at 60°C for 2 h to form aqua complex of dichloro dioxo molybdenum (Mo0 2 Cl 2 .2H 2 0). This complex was extracted with diethyl ether (30 ml x 5). The combined ether layer was concentrated under reduced pressure. To the same solution was added 50 ml dried LLS 211
  • Molybdenum trioxide (Mo0 3, 1.44gm, 10 mmol) was reacted with cone, aqueous hydrochloric (7 ml, 35%) acid at 60°C for 2 h to form aqua complex of dichloro dioxo molybdenum (Mo0 2 CI 2 .2H 2 0). This complex was extracted with diethyl ether (30 ml x 5). The combined ether layer was concentrated under reduced pressure. To the same solution was added 50 ml dried THF and remaining ether was removed under reduced pressure.
  • Molybdenum trioxide (Mo0 3> 1.30gm, 9 mmol) was reacted with cone, aqueous hydrochloric (7ml, 35%) acid at 60°C for 2 h to form aqua complex of dichloro dioxo molybdenum (Mo0 2 CI 2 .2H 2 0).
  • DMF N-dimethyl formamide
  • CopMo0 2 CI prepared in first step was added to THF solution of freshly prepared lithium salt of phenyl acetylene at -78 9 C and the LLS 211 solution was warmed up to 30°C and further stirred for 3 h at 30°C.
  • the unreacted butyl lithium was quenched by NH 4 OH solution and the solvent was removed under vacuum.
  • the cyclopentadienyl dioxo molybdenum acetylide complex as prepared in example 1 was used as catalyst for catalytic oxidation of cyclohexene.
  • Cyclohexene (0.820 g, 10 mmol), hydrogen peroxide (11 mmol, 30 % aqueous) and catalyst (O.lmmol, 30mg) was heated to 80 9 C in acetonitrile for 8 h giving 100 % conversion of cyclohexene.
  • the products obtained were cyclohexene oxide (40%), trans cyclohexane diol (17%), 2- cyclohexenol (23%), 2-cyclohexenone (20%).
  • the cyclopentadienyl dioxo molybdenum acetylide complex as prepared in example 2 was used as catalyst for catalytic oxidation of activated alcohols.
  • Benzyl alcohol (10 mmol), hydrogen peroxide (20 mmol) and catalyst (O.lmmol, 30mg) was heated at 80°C for 8 h giving 86% conversion with 92% selectivity for benzaldehyde and 8% selectivity for benzoic acid.
  • the cyclopentadienyl dioxo molybdenum acetylide complex as prepared in example 3 was used as catalyst for catalytic oxidation of various anilines.
  • Aniline (10 mmol), hydrogen peroxide (20 mmol) catalyst (O.lmmol, 30mg) was stirred at 30°C for 12h giving 97% aniline conversion and 97% selectivity for nitrosobenzene.
  • the cyclopentadienyl dioxo molybdenum acetylide complex as prepared in example 4 was used as catalyst for catalytic oxidation of various sulfides including refractory sulfides using hydrogen peroxide.
  • catalyst O.lmmol, 30mg
  • the cyclopentadienyl dioxo molybdenum acetylide complex as prepared in example 1 was used as catalyst for catalytic oxidation of ethyl benzene.
  • TBHP t-butyl hydrogen peroxide
  • catalyst O.lmmol, 30mg

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un complexe de molybdène acétylide dioxo organométallique de formule (η5-C5H5)MoO2(-CsΞCPh) et concerne un procédé simple, court et efficace pour la synthèse du complexe de molybdène dioxo organométallique qui est utilisé comme catalyseur pour un certain nombre de réactions d'oxydation.
EP11776595.8A 2010-09-14 2011-09-14 Complexe de molybdène acétylide dioxo organométallique et procédé de préparation associé Withdrawn EP2616475A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN2177MU2010 2010-09-14
PCT/IN2011/000627 WO2012035555A1 (fr) 2010-09-14 2011-09-14 Complexe de molybdène acétylide dioxo organométallique et procédé de préparation associé

Publications (1)

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EP2616475A1 true EP2616475A1 (fr) 2013-07-24

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EP11776595.8A Withdrawn EP2616475A1 (fr) 2010-09-14 2011-09-14 Complexe de molybdène acétylide dioxo organométallique et procédé de préparation associé

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EP (1) EP2616475A1 (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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See references of WO2012035555A1 *

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