WO2016199174A1 - Oxidative dehydrogenation of lactate esters to pyruvate esters - Google Patents

Oxidative dehydrogenation of lactate esters to pyruvate esters Download PDF

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WO2016199174A1
WO2016199174A1 PCT/IN2016/050181 IN2016050181W WO2016199174A1 WO 2016199174 A1 WO2016199174 A1 WO 2016199174A1 IN 2016050181 W IN2016050181 W IN 2016050181W WO 2016199174 A1 WO2016199174 A1 WO 2016199174A1
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lactate
pyruvate
catalyst
ethyl
ethyl lactate
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WO2016199174A4 (en
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Shubhangi Bhalchandra Umbarkar
Mohan Keraba Dongare
Swati Laxmikantrao PANDHARE
Sonali Balasaheb KHOMANE
Dhananjay Shahauraj DOKE
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Council of Scientific and Industrial Research CSIR
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups

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  • the present invention relates to an oxidative dehydrogenation process for the synthesis of pyruvates from lactates. More particularly, the present invention relates to a process for the synthesis of pyruvates from lactates with 100% selectivity towards pyruvates.
  • Pyruvic acid and pyruvates are important intermediates for perfumes, food additives, and electronic materials as well as raw materials for various bioactive substances such as antiviral drugs. It is used as flavours for food.
  • pyruvic acid is produced by dehydrative decarboxylation of tartaric acid.
  • Silica-supported pyrosulfate catalyst (K2S2O7/S1O2) is used for synthesis of ethyl pyruvate in continuous mode with up to 60% yields at the high temperature of 300 °C.
  • KHSO4 as a dehydrating agent
  • Pyruvate can also be obtained by a microbial process, using strains of yeast and E. coli. However, both strains require precise regulation of media composition during fermentation and complex supplements.
  • US Pat. No. 5053527 discloses a process for the manufacture of alkyl pyruvates having the general formula: CH3— CO— COOR; wherein R represents a C1-C8 alkyl radical, by oxidation of the corresponding alkyl lactate, the improvement comprising; admixing a 30 to 70% by weight aqueous hydrogen peroxide solution into a solution of the alkyl lactate in an organic water-immiscible solvent containing a catalytic quantity of bromine while maintaining a temperature of 15°-30° C.
  • VOCl 3 vanadium oxytrichloride
  • Chinese Pat. No. 1060759 discloses the catalytic oxidation synthesis of pyruvate is characterized by that in the presence of modified silver or copper catalyst said invention uses gas phase atmospheric oxidation of lactate to prepare pyruvate.
  • Its dressing agent is a halide, and one or several kinds of P, Zr, Zn and K also can be added.
  • Its reaction temp is 300-600 deg. C, and according to different technological processes, the crude pyruvate products with low concentration and high concentration can be respectively prepared, and after rectification the invented refined product can be obtained.
  • pyruvic acid esters for example ethyl lactate, petroleum ether, sodium dihydrogen phosphate, potassium permanganate reacted together, with potassium permanganate as the oxidizing agent lactate, and acetone esters evaporated. Also some hydrogen peroxide as an oxidant lactate production and pyruvate.
  • Such methods are adding an oxidizing agent in the lactate ester in the liquid phase oxidation of lactate to pyruvate, and then isolated and purified.
  • alkyl pyruvates are prepared by oxidizing alkyl lactates in the presence of a silver catalyst of a defined particle size, at from 450° to 700° C. The products are starting materials for the preparation of drugs, synthetic resins and plastics.
  • US Pat. No. 887795 reports a method for preparing a pyruvate ester is disclosed. In the method of the present invention, a lactate ester is oxidized by hydrogen peroxide in the presence of a Ti— Si molecular sieve catalyst.
  • the Ti— Si molecular sieve catalyst is easily filtered and recycled, the reaction conditions are mild due to the usage of hydrogen peroxide, the process is simple and easily performed, the conversion rate of the lactate ester is high, and the selectivity of the pyruvate ester is high-
  • Chinese Pat. No. 104276951 discloses an aqueous-phase catalytic oxidation method for preparing lactate pyruvate, Pt load which bismuth compound or Pd as catalyst and molecular oxygen as oxidant, water as solvent, the selective and efficient preparation of pyruvate oxidation lactates, The process mild reaction conditions, high selectivity, the catalyst can be reused, has important application prospects.
  • Chinese Pat. No. 1359893 discloses a process for preparing ethyl pyruvate is characterized by that the reaction of the mixture of ethyl lactate vapour and air at 250-300 deg. C in the presence of silica gel carried silver catalyst. Its advantages are high conversion (80%) and selectivity (90%), and high activity and selectivity of catalyst. Therefore, there is a need to develop a suitable catalyst for high yield synthesis of ethyl pyruvate from ethyl lactate.
  • the main objective of the present invention is to provide a simple one step oxidative dehydrogenation process for the synthesis of pyruvates from lactates with selectivity and yields for pyruvates.
  • Another objective of the present invention is to provide a simple process for the synthesis of pyruvates from lactates with 100% selectivity in presence of easily available catalysts and oxidizing agent.
  • the present invention provides a simple one step oxidative dehydrogenation process for the synthesis of alkyl pyruvate comprising reacting an alkyl lactate with peroxides in the presence of catalyst at the temperature ranging from 25-100 deg C for the time period ranging from 5 to 40 hours in an organic solvent to afford alkyl pyruvate.
  • said alkyl lactates are selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, butyl lactate and such like.
  • said solvent is selected from the group consisting of water, acetonitrile, methanol, ethanol and toluene.
  • said catalyst is selected from salts of transition metals.
  • said metals are in the form of salts, oxides and hydroxides.
  • said metals are selected from the group consisting of Co, Cr, Fe, Mo, V, W, Ti, Cu, Cr, Ru, Mn, Ag, Au, Ni, Pd, or Pt.
  • said peroxides are selected from the group consisting of tert-butyl hydrogen peroxide and meta chloro perbenzoic acid.
  • said process of the invention for the synthesis of alkyl pyruvates results in > 90% selectivity towards the pyruvates.
  • said process provides 100% selectivity towards the pyruvates. In still yet another embodiment, said process provides upto 98% conversion of alkyl lactates.
  • the present invention relates to a simple one step oxidative dehydrogenation process for the synthesis of alkyl pyruvate with 100% selectivity towards alkyl pyruvate comprising reacting an alkyl lactate in the presence of catalyst at the temperature ranging from 25- 100°C for the time period ranging from 5 to 40 hours in an organic solvent and peroxide to afford alkyl pyruvate.
  • R Alkyl group
  • said alkyl lactates are selected from methyl lactate, ethyl lactate, propyl lactate, butyl lactate and such like.
  • said solvent is selected from water, acetonitrile, methanol, ethanol and toluene.
  • said process is carried out with solvent or without solvent.
  • said catalyst is selected from salts of transition metals.
  • said metals are in the form of salts, oxides and hydroxides.
  • said metals are Co, Cr, Fe, Mo, V, W, Ti, Cu, Cr, Ru, Mn, Ag, Au, Ni, Pd, or Pt.
  • said peroxides are selected from tert-butyl hydrogen peroxide, m-chloroperbenzoic acid.
  • said process of the invention for the synthesis of alkyl pyruvates results in > 90% selectivity towards the pyruvates.
  • said process provides 100% selectivity towards the pyruvates. In still another embodiment, said process provides upto 98% conversion of alkyl lactates.
  • DMSO dimethylsulfoxide
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.030 g M0O2CI2.2DMSO as catalyst.
  • the solution was heated at 80 °C for 19 h. In this reaction 92% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0276g M0O2CI2 (bipy) as catalyst.
  • the solution was heated at 80 °C for 19 h. In this reaction 19% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst.
  • the solution was heated at 80 °C for 17 h. In this reaction 96% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2.(benzthiozole)2 as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0276 g Mo02Cl2.2benzthiozole as catalyst.
  • the solution was heated at 80 °C for 15 h. In this reaction 70% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using M0O3 as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0276g M0O3 as catalyst.
  • the solution was heated at 80 °C for 17 h. In this reaction 36% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using VO(acac)2 as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0215g VO(acac)2 as catalyst.
  • the solution was heated at 80 °C for 15 h. In this reaction 80% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Example 7 Example 7:
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using copper acetate as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.009 lg Copper acetate as catalyst.
  • the solution was heated at 80 °C for llh. In this reaction 46% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5g methyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0330g Mo02Cl2(DMF)2 as catalyst.
  • the solution was heated at 80 °C for 14 h. In this reaction 43% conversion of methyl lactate was obtained with 100% selectivity for methyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, no solvent, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst.
  • the solution was kept at room temperature for 36h. In this reaction 3% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst.
  • the solution was heated at 50°C for 11 h. In this reaction 6% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using cobalt (II) chloride as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0199g cobalt (II) chloride as catalyst.
  • the solution was heated at 80 °C for llh. In this reaction 82% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0144g Mo02Ci2.(DMF)2 (lmol%) as catalyst.
  • the solution was heated at 80 °C for 11 h. In this reaction 56% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0072g Mo02Ci2.(DMF) 2 (0.5mol%) as catalyst.
  • the solution was heated at 80 °C for 11 h. In this reaction 11 % conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0722g Mo02Ci2.(DMF)2 (5mol%) as catalyst.
  • the solution was heated at 80 °C for 11 h. In this reaction 72% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Example 15 Example 15:
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst.
  • the solution was kept at room temperature for 38h. In this reaction 6% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using as Iron(III) Chloride catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0137g Iron(III) Chloride as catalyst.
  • the solution was heated at 80 °C for 9h. In this reaction 63% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, no solvent, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst.
  • the solution was heated at 80 °C for 10 h. In this reaction 27% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Silver nitrate as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0143g silver nitate as catalyst.
  • the solution was heated at 80 °C for 10 h. In this reaction 62% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Example 19 Example 19:
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Palladium (II) acetate as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0189g Palladium (II) acetate as catalyst.
  • the solution was heated at 80 °C for l lh. In this reaction 36% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using platinum (II) acetylacetone as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0332g platinum (II) acetylacetone as catalyst.
  • the solution was heated at 80 °C for 9h. In this reaction 56% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using gold chloride as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0256g gold chloride as catalyst.
  • the solution was heated at 80 °C for 24h. In this reaction 94% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using nickel chloride as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0109g nickel chloride as catalyst.
  • the solution was heated at 80 °C for 24h. In this reaction 96% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using ruthenium acetylacetonate as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0337g ruthenium acetylacetonate as catalyst.
  • the solution was heated at 80 °C for lOh. In this reaction 50% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using potassium dicromate as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0248g potassium dicromate as catalyst.
  • the solution was heated at 80 °C for lOh. In this reaction 68% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using sodium tungstate as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0279g sodium tungstate as catalyst.
  • the solution was heated at 80 °C for lOh. In this reaction 12% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using potassium titanium oxalate as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0299g potassium titanium oxalate as catalyst.
  • the solution was heated at 80 °C for lOh. In this reaction 10% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
  • Example 27 Example 27:
  • Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using VO(acac) 2 as catalyst.
  • a 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.4 g meta chloro perbenzoic acid (MCPBA) and 0.0215g VO(acac) 2 as catalyst.
  • MCPBA meta chloro perbenzoic acid
  • the solution was heated at 80 °C for 24 h. In this reaction 50% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.

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Abstract

The present invention relates to a simple one step oxidative dehydrogenation process for the synthesis of alkyl pyruvate with 100% selectivity towards alkyl pyruvate comprising reacting an alkyl lactate in the presence of catalyst at the temperature ranging from 25-100°C for the time period ranging from 5 to 40 hours in an organic solvent and hydrogen peroxide to afford alkyl pyruvate.

Description

OXIDATIVE DEHYDROGENATION OF LACTATE ESTERS TO
PYRUVATE ESTERS
FIELD OF THE INVENTION:
The present invention relates to an oxidative dehydrogenation process for the synthesis of pyruvates from lactates. More particularly, the present invention relates to a process for the synthesis of pyruvates from lactates with 100% selectivity towards pyruvates.
BACKGROUND AND PRIOR ART OF THE INVENTION:
Pyruvic acid and pyruvates (pyruvic acid esters) are important intermediates for perfumes, food additives, and electronic materials as well as raw materials for various bioactive substances such as antiviral drugs. It is used as flavours for food.
Conventionally pyruvic acid is produced by dehydrative decarboxylation of tartaric acid. Silica-supported pyrosulfate catalyst (K2S2O7/S1O2) is used for synthesis of ethyl pyruvate in continuous mode with up to 60% yields at the high temperature of 300 °C. This reaction requires excess KHSO4 as a dehydrating agent, leading to an expensive and wasteful process. Pyruvate can also be obtained by a microbial process, using strains of yeast and E. coli. However, both strains require precise regulation of media composition during fermentation and complex supplements.
Article titled "New technique on synthesis of ethyl pyruvate" by Chen Sufang et al. reports ethyl pyruvate was synthesized from ethyl lactate using TBHP as oxidant and TBAB as phase transfer catalyst, the purity of product was over 98 %.The reaction is environment friendly and easy to operate,it provides a new method to synthesize ethyl pyruvate from ethyl lactate.
US Pat. No. 5053527 discloses a process for the manufacture of alkyl pyruvates having the general formula: CH3— CO— COOR; wherein R represents a C1-C8 alkyl radical, by oxidation of the corresponding alkyl lactate, the improvement comprising; admixing a 30 to 70% by weight aqueous hydrogen peroxide solution into a solution of the alkyl lactate in an organic water-immiscible solvent containing a catalytic quantity of bromine while maintaining a temperature of 15°-30° C. Article titled "Titania-catalysed oxidative dehydrogenation of ethyl lactate: effective yet selective free-radical oxidation" by Enrique V. Ramos -Fernandez et al. published in Green Chemistry, 2014, 16, pp 3358 reports the catalytic oxidative dehydrogenation of ethyl lactate, as an alternative route to ethyl pyruvate. Testing various solid catalysts (Fe203, Ti02, V205/MgO-Al203, Zr02, Ce02 and ZnO). The liquid phase oxidation of ethyl lactate 1 was carried out in a 400 ml stirred autoclave (Biometa, fitted with a system for liquid sampling) at 403 K and at constant pressure of 1 MPa of pure oxygen. The catalyst (2 g) was immersed in 200 g of ethyl lactate. In experiments using a solvent, mass ratio of 1 : 1 (solvent : reactant) was used.
Article titled "Catalytic activity of iron phosphate doped with a small amount of molybdenum in the oxidative dehydrogenation of lactic acid to pyruvic acid" by Mamoru Ai published in Applied Catalysis A General 234(l):235-243 reports both the catalytic activity and the selectivity of iron phosphate in the oxidative dehydrogenation of lactic acid to form pyruvic acid increase dramatically by doping a very small amount of molybdenum compounds. Both the highest activity and selectivity are obtained at a Mo/Fe atomic ratio ranging from 0.01 to 0.3. The catalytic activity and selectivity are not affected if the source of Mo6+ is changed. Effects similar to those for the Mo6+ doping are not observed in the cases of the doping of V5+ or W6+. The functions of Mo6+ were studied.
Article titled "Efficient oxidative dehydrogenation of lactate to pyruvate using a gas-liquid micro flow system" by Toshiya Yasukawa et al. published in Industrial and Engineering Chemistry Research, 2011, 50 (7), pp 3858-3863 reports an efficient production of pyruvate by the oxidative dehydrogenation of lactate is achieved using a micro flow system based on gas-liquid slug flow. In this micro flow system, oxidizing agents and acetonitrile solutions of lactates and vanadium species are used, and lactate is converted into the corresponding pyruvate. For reasons of atom economy and enhanced mass transfer of oxygen into the liquid phase, due to internal circulation flow within slugs, molecular oxygen is the preferred agent. In a catalyst screening, vanadium oxytrichloride (VOCl3) gave the highest pyruvate yield. A continuous system is developed, consisting of the following two processes using T-shaped mixers: the mixing of an acetonitrile solution of lactate with that of VOCI3 and the injection of oxygen gas into the solution mixture. Compared with the conventional batch system, the oxidative dehydrogenation of lactate to the corresponding pyruvate proceeds more effectively using this micro flow system.
Chinese Pat. No. 1060759 discloses the catalytic oxidation synthesis of pyruvate is characterized by that in the presence of modified silver or copper catalyst said invention uses gas phase atmospheric oxidation of lactate to prepare pyruvate. Its dressing agent is a halide, and one or several kinds of P, Zr, Zn and K also can be added. Its reaction temp, is 300-600 deg. C, and according to different technological processes, the crude pyruvate products with low concentration and high concentration can be respectively prepared, and after rectification the invented refined product can be obtained. There are a variety of methods known in the art for preparing pyruvic acid esters, for example ethyl lactate, petroleum ether, sodium dihydrogen phosphate, potassium permanganate reacted together, with potassium permanganate as the oxidizing agent lactate, and acetone esters evaporated. Also some hydrogen peroxide as an oxidant lactate production and pyruvate. Such methods are adding an oxidizing agent in the lactate ester in the liquid phase oxidation of lactate to pyruvate, and then isolated and purified.
US Pat. No. 4229590 reports alkyl pyruvates are prepared by oxidizing alkyl lactates in the presence of a silver catalyst of a defined particle size, at from 450° to 700° C. The products are starting materials for the preparation of drugs, synthetic resins and plastics. US Pat. No. 887795 reports a method for preparing a pyruvate ester is disclosed. In the method of the present invention, a lactate ester is oxidized by hydrogen peroxide in the presence of a Ti— Si molecular sieve catalyst. In the present invention, the Ti— Si molecular sieve catalyst is easily filtered and recycled, the reaction conditions are mild due to the usage of hydrogen peroxide, the process is simple and easily performed, the conversion rate of the lactate ester is high, and the selectivity of the pyruvate ester is high- Chinese Pat. No. 104276951 discloses an aqueous-phase catalytic oxidation method for preparing lactate pyruvate, Pt load which bismuth compound or Pd as catalyst and molecular oxygen as oxidant, water as solvent, the selective and efficient preparation of pyruvate oxidation lactates, The process mild reaction conditions, high selectivity, the catalyst can be reused, has important application prospects.
Chinese Pat. No. 1359893 discloses a process for preparing ethyl pyruvate is characterized by that the reaction of the mixture of ethyl lactate vapour and air at 250-300 deg. C in the presence of silica gel carried silver catalyst. Its advantages are high conversion (80%) and selectivity (90%), and high activity and selectivity of catalyst. Therefore, there is a need to develop a suitable catalyst for high yield synthesis of ethyl pyruvate from ethyl lactate.
OBJECTIVE OF THE INVENTION:
The main objective of the present invention is to provide a simple one step oxidative dehydrogenation process for the synthesis of pyruvates from lactates with selectivity and yields for pyruvates.
Another objective of the present invention is to provide a simple process for the synthesis of pyruvates from lactates with 100% selectivity in presence of easily available catalysts and oxidizing agent.
SUMMARY OF THE INVENTION:
Accordingly, the present invention provides a simple one step oxidative dehydrogenation process for the synthesis of alkyl pyruvate comprising reacting an alkyl lactate with peroxides in the presence of catalyst at the temperature ranging from 25-100 deg C for the time period ranging from 5 to 40 hours in an organic solvent to afford alkyl pyruvate. In an embodiment, said alkyl lactates are selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, butyl lactate and such like.
In another embodiment, said solvent is selected from the group consisting of water, acetonitrile, methanol, ethanol and toluene.
In still another embodiment, said catalyst is selected from salts of transition metals.
In a preferred embodiment, said metals are in the form of salts, oxides and hydroxides. In another preferred embodiment, said metals are selected from the group consisting of Co, Cr, Fe, Mo, V, W, Ti, Cu, Cr, Ru, Mn, Ag, Au, Ni, Pd, or Pt. In still another preferred embodiment, said peroxides are selected from the group consisting of tert-butyl hydrogen peroxide and meta chloro perbenzoic acid.
In yet another embodiment, said process of the invention for the synthesis of alkyl pyruvates results in > 90% selectivity towards the pyruvates.
In a preferred embodiment, said process provides 100% selectivity towards the pyruvates. In still yet another embodiment, said process provides upto 98% conversion of alkyl lactates.
DETAILED DESCRIPTION OF THE INVENTION:
The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.
The present invention relates to a simple one step oxidative dehydrogenation process for the synthesis of alkyl pyruvate with 100% selectivity towards alkyl pyruvate comprising reacting an alkyl lactate in the presence of catalyst at the temperature ranging from 25- 100°C for the time period ranging from 5 to 40 hours in an organic solvent and peroxide to afford alkyl pyruvate.
Temp, Solvent
Figure imgf000006_0001
R = Alkyl group
In preferred embodiment, said alkyl lactates are selected from methyl lactate, ethyl lactate, propyl lactate, butyl lactate and such like.
In another preferred embodiment, said solvent is selected from water, acetonitrile, methanol, ethanol and toluene.
In still yet another preferred embodiment, said process is carried out with solvent or without solvent.
In still another preferred embodiment, said catalyst is selected from salts of transition metals. In yet another preferred embodiment, said metals are in the form of salts, oxides and hydroxides.
In still yet another preferred embodiment, said metals are Co, Cr, Fe, Mo, V, W, Ti, Cu, Cr, Ru, Mn, Ag, Au, Ni, Pd, or Pt.
In still yet another preferred embodiment, said peroxides are selected from tert-butyl hydrogen peroxide, m-chloroperbenzoic acid.
In an embodiment, said process of the invention for the synthesis of alkyl pyruvates results in > 90% selectivity towards the pyruvates.
In another embodiment, said process provides 100% selectivity towards the pyruvates. In still another embodiment, said process provides upto 98% conversion of alkyl lactates.
The following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purpose of illustrative discussion of preferred embodiments of the invention.
EXAMPLES:
Example 1:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMSO)2; (DMSO = dimethylsulfoxide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.030 g M0O2CI2.2DMSO as catalyst. The solution was heated at 80 °C for 19 h. In this reaction 92% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 2:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using M0O2CI2 bipy; (bipy = bipyridine) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0276g M0O2CI2 (bipy) as catalyst. The solution was heated at 80 °C for 19 h. In this reaction 19% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate
Example 3:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst. The solution was heated at 80 °C for 17 h. In this reaction 96% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 4:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2.(benzthiozole)2 as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0276 g Mo02Cl2.2benzthiozole as catalyst. The solution was heated at 80 °C for 15 h. In this reaction 70% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 5:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using M0O3 as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0276g M0O3 as catalyst. The solution was heated at 80 °C for 17 h. In this reaction 36% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 6:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using VO(acac)2 as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0215g VO(acac)2 as catalyst. The solution was heated at 80 °C for 15 h. In this reaction 80% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate. Example 7:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using copper acetate as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.009 lg Copper acetate as catalyst. The solution was heated at 80 °C for llh. In this reaction 46% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 8:
Oxidative dehydrogenation of methyl lactate to methyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5g methyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0330g Mo02Cl2(DMF)2 as catalyst. The solution was heated at 80 °C for 14 h. In this reaction 43% conversion of methyl lactate was obtained with 100% selectivity for methyl pyruvate.
Example 9:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, no solvent, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst. The solution was kept at room temperature for 36h. In this reaction 3% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 10:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst. The solution was heated at 50°C for 11 h. In this reaction 6% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate. Example 11:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using cobalt (II) chloride as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0199g cobalt (II) chloride as catalyst. The solution was heated at 80 °C for llh. In this reaction 82% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 12:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0144g Mo02Ci2.(DMF)2 (lmol%) as catalyst. The solution was heated at 80 °C for 11 h. In this reaction 56% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 13:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0072g Mo02Ci2.(DMF)2 (0.5mol%) as catalyst. The solution was heated at 80 °C for 11 h. In this reaction 11 % conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 14:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0722g Mo02Ci2.(DMF)2 (5mol%) as catalyst. The solution was heated at 80 °C for 11 h. In this reaction 72% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate. Example 15:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst. The solution was kept at room temperature for 38h. In this reaction 6% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 16:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using as Iron(III) Chloride catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0137g Iron(III) Chloride as catalyst. The solution was heated at 80 °C for 9h. In this reaction 63% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 17:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Mo02Cl2(DMF)2; (DMF = dimethyl formamide) as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, no solvent, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.029 lg Mo02Ci2.(DMF)2 as catalyst. The solution was heated at 80 °C for 10 h. In this reaction 27% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 18:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Silver nitrate as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0143g silver nitate as catalyst. The solution was heated at 80 °C for 10 h. In this reaction 62% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate. Example 19:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using Palladium (II) acetate as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0189g Palladium (II) acetate as catalyst. The solution was heated at 80 °C for l lh. In this reaction 36% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 20:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using platinum (II) acetylacetone as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0332g platinum (II) acetylacetone as catalyst. The solution was heated at 80 °C for 9h. In this reaction 56% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 21:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using gold chloride as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0256g gold chloride as catalyst. The solution was heated at 80 °C for 24h. In this reaction 94% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 22:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using nickel chloride as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0109g nickel chloride as catalyst. The solution was heated at 80 °C for 24h. In this reaction 96% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate. Example 23:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using ruthenium acetylacetonate as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert -butyl hyrogenperoxide (5-6 M in decane) and 0.0337g ruthenium acetylacetonate as catalyst. The solution was heated at 80 °C for lOh. In this reaction 50% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 24:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using potassium dicromate as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0248g potassium dicromate as catalyst. The solution was heated at 80 °C for lOh. In this reaction 68% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 25:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using sodium tungstate as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0279g sodium tungstate as catalyst. The solution was heated at 80 °C for lOh. In this reaction 12% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Example 26:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using potassium titanium oxalate as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.5 mL tert-butyl hyrogenperoxide (5-6 M in decane) and 0.0299g potassium titanium oxalate as catalyst. The solution was heated at 80 °C for lOh. In this reaction 10% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate. Example 27:
Oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out using VO(acac)2 as catalyst. A 50 ml two necked round bottom flask was charged with 0.5 g ethyl lactate, 10 g acetonitrile, 1.4 g meta chloro perbenzoic acid (MCPBA) and 0.0215g VO(acac)2 as catalyst. The solution was heated at 80 °C for 24 h. In this reaction 50% conversion of ethyl lactate was obtained with 100% selectivity for ethyl pyruvate.
Following table 1 shows catalytic activity data for lactate to pyruvate.
Table 1: Catalytic activity data for lactate to pyruvate
Figure imgf000015_0001
ADVANTAGES OF THE PRESENT INVENTION
• Mild reaction conditions
• Very high conversion upto 98%
• Very high selectivity upto 100%
• No polymerization observed

Claims

WE CLAIM:
1. A simple one step oxidative dehydrogenation process for the synthesis of alkyl pyruvate with 100% selectivity towards alkyl pyruvate comprising reacting an alkyl lactate in the presence of catalyst at the temperature ranging from 25-100°C for the time period ranging from 5 to 40 hours in an organic solvent and peroxides to afford alkyl pyruvate.
2. The process as claimed in claim 1, wherein said alkyl lactates are selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
3. The process as claimed in claim 1, said solvent is selected from the group consisting of water, acetonitrile, methanol, ethanol and toluene.
4. The process as claimed in claim 1, wherein said process is carried out with solvent or without solvent.
5. The process as claimed in claim 1, wherein said catalyst is selected from salts of alkali and transition metals; said metals are in the form of salts, oxides and hydroxides; said metals are selected from the group consisting of Co, Cr, Fe, Mo, V, W, Ti, Cu, Cr, Ru, Mn, Ag, Au, Ni, Pd, or Pt.
6. The process as claimed in claim 1, wherein said peroxides is selected from the group consisting of tert-butyl hydrogen peroxide and meta chloro perbenzoic acid.
7. The process as claimed in claim 1, wherein said process has selectivity towards the pyruvates is greater than 90%; said process has selectivity towards the pyruvates is 100%.
8. The process as claimed in claim 1, wherein said process provides greater than 90% conversion of alkyl lactates.
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