- Sustainable Continuous Flow Valorization of Γ-Valerolactone with Trioxane to Α-Methylene-Γ-Valerolactone over Basic Beta Zeolites
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The need for more sustainable products and processes has led to the use of new methodologies with low carbon footprints. In this work, an efficient tandem process is demonstrated for the liquid-phase catalytic upgrading of lignocellulosic biomass-derived γ-valerolactone (GVL) with trioxane (Tx) to α-methylene-γ-valerolactone (MeGVL) in flow system using Cs-loaded hierarchical beta zeolites. The introduction of mesopores along with the presence of basic sites of mild strength leads to MeGVL productivity 20 times higher than with the bulk beta zeolite, reaching 0.325 mmol min?1 gcat?1 for the best-performing catalyst, the highest value reported so far. This catalyst proves stable upon reuse in consecutive cycles, which is ascribed to the partial depletion of the basic sites. The obtained MeGVL is subjected to visible-light-induced polymerization, resulting in a final material with similar properties to the widely used poly(methyl) methacrylate.
- Al-Naji, Majd,Puértolas, Bego?a,Kumru, Baris,Cruz, Daniel,B?umel, Marius,Schmidt, Bernhard V. K. J.,Tarakina, Nadezda V.,Pérez-Ramírez, Javier
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- Calcium(II)- And Triflimide-Catalyzed Intramolecular Hydroacyloxylation of Unactivated Alkenes in Hexafluoroisopropanol
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We report an efficient intramolecular hydroacyloxylation of unactivated alkenes, offering a streamlined access to relevant γ-lactones, which features the utilization of either a calcium(II) salt or triflimide as a catalyst in hexafluoroisopropanol. This method could be applied to the synthesis of natural products and the late-stage functionalization of natural and bioactive molecules. Additionally, DFT computations were used to elucidate the twist of reactivity observed between the hydroamidation and hydroacyloxylation of unactivated alkenes regarding the formation of 5- and 6-membered rings.
- Qi, Chenxiao,Yang, Shengwen,Gandon, Vincent,Leb?uf, David
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supporting information
p. 7405 - 7409
(2019/10/02)
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- METHOD FOR PRODUCING CYCLIC UNSATURATED COMPOUND
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The present invention provides a method for producing a cyclic unsaturated compound, which sufficiently suppresses generation of acyclic unsaturated compounds and permits excellent yield and reaction rate. Such a method for producing a cyclic unsaturated compound is a method for producing a cyclic unsaturated compound by reacting an a, ?-unsaturated carboxylic acid with an unsaturated organic compound, wherein the method comprises a step of reacting the a, ?-unsaturated carboxylic acid with the unsaturated organic compound in the presence of a catalyst.
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Page/Page column 83, 92
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- Liquid phase synthesis of methylene lactones using novel grafted catalyst
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Process for converting certain lactones to their alpha-methylene substituted forms that exhibits high conversion and selectivity.
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- Liquid phase synthesis of methylene lactones using novel catalyst
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Process for converting certain lactones to their alpha-methylene derivatives in the liquid phase with both high conversion and selectivity using easily recoverable novel heterogeneous catalysts.
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Page/Page column 5-6
(2008/06/13)
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- Liquid phase synthesis of methylene lactones using oxnitride catalyst
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Process for converting certain lactones to their alpha-methylene derivatives in the liquid phase using oxynitride catalysts or composite catalysts incorporating dithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, or barium or combinations thereof.
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Page/Page column 5
(2010/02/15)
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- Gas phase synthesis of methylene lactones using novel catalyst
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Process for converting certain lactones to their alpha-methylene substituted forms that not only exhibits high initial activity (conversion), but also maintains a high level of activity with time on stream.
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Page/Page column 5
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- Gas phase synthesis of methylene lactones using oxinitride catalyst
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Process for converting certain lactones to their alpha-methylene substituted forms using an oxynitride catalyst or a composite oxynitride catalyst incorporating lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, or barium or combinations thereof.
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Page/Page column 5
(2008/06/13)
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- Gas phase synthesis of methylene lactones using novel grafted catalyst
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Process for converting certain lactones to their alpha-methylene substituted forms that not only exhibits high initial activity (conversion), but also maintains a high level of activity with time on stream.
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Page/Page column 7
(2008/06/13)
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- Integrated two-step process for the production of gamma-methyl-alpha-methylene-gamma-butyrolactone from levulinic acid and hydrogen
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An integrated two step method for making gamma-methyl alpha-methylene-gamma-butyrolactone (meMBL) from levulinic acid, in which levulinic acid is reacted with hydrogen in the first step to form a crude reaction product containing gamma-valerolactone, and the crude reaction product, without removal of unreacted levulinic acid therefrom, is reacted with formaldehyde in the second step to produce MeMBL.
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Page/Page column 2; 3
(2008/06/13)
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- Supercritical fluid phase synthesis of methylene lactones using oxynitride catlayst
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Process for converting certain lactones to their alpha-methylene substituted forms in a supercritical or near-critical fluid phase reaction using an oxynitride catalyst or a composite oxynitride catalyst incorporating lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, or barium or combinations thereof.
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Page/Page column 6
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- Supercritical fluid phase synthesis of methylene lactones using novel catalyst field of invention
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Process for converting certain lactones to their alpha-methylene substituted forms that not only exhibits high initial activity (conversion), but also provides high reactor productivity (mass of product per mass of catalyst per unit of time) and sustained maintenance of a high level of activity and productivity with time on stream.
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Page/Page column 10-11
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- Process for the production of Y-methyl-A-methylene-Y-butyrolactone from reaction of levulinic acid and hydrogen in the liquid phase followed by reaction of crude-Y-valerolactone and formaldehyde
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An integrated two-step process for the production of gamma-methyl-alpha-methylene-gamma-butyrolactone from reaction of levulinic acid and hydrogen in the liquid phase to produce a crude GVL-containing product, followed by reaction of the crude GVL-containing product and formaldehyde in the supercritical or near-critical fluid phase.
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Page/Page column 4; 5
(2008/06/13)
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- Process for the production of y-methyl-a-methylene-y-butyrolactone from reaction of levulinic acid and hydrogen with recycle of unreacted levulinic acid followed by reaction of crude y-valerolactone and formaldehyde, both reactions being carried out in the supercritical or near-critical fluid phase
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Process for the production of γ-methyl-α-methylene-γ-butyrolactone from reaction of levulinic acid and hydrogen with recycle of unreacted levulinic acid and reaction of crude γ-valerolactone and formaldehyde, both reactions being carried out in the supercritical or near-critical fluid phase.
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Page/Page column 4; 5
(2008/06/13)
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- Process for the production of y-methyl-a-methylene-y-butyrolactone from reaction of levulinic acid and hydrogen followed by reaction of crude y-valerolactone and formaldehyde, both reactions being carried out in the supercritical or near-critical fluid phase
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Process for the production of γ-methyl-α-methylene-γ-butyrolactone from reaction of levulinic acid and hydrogen followed by reaction of crude γ-valerolactone and formaldehyde, both reactions being carried out in the supercritical or near-critical fluid phase.
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Page/Page column 4
(2008/06/13)
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- Supercritical fluid phase synthesis of methylene lactones using novel grafted catalyst
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Process for converting certain lactones to their alpha-methylene substituted forms in a supercritical or near-critical fluid phase reaction using a novel grafted catalyst that not only exhibits high initial activity (conversion), but also maintains a high level of activity with time on stream.
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Page/Page column 7
(2010/02/15)
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- Novel synthesis, cytotoxic evaluation, and structure-activity relationship studies of a series of α-alkylidene-γ-lactones and lactams
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5-Alkyl- and 5-arylalkyl-3-methylenedihydrofuran-2-ones 13a-e, 3-alkylidenedihydrofuran-2-ones 18a-c, and 3-methylenepyrrolidin-2-ones 16a-e were synthesized utilizing ethyl 2-diethoxyphosphoryl-4-nitroalkanoates 9a-e as common intermediates. All obtained
- Janecki, Tomasz,B?aszczyk, Edyta,Studzian, Kazimierz,Janecka, Anna,Krajewska, Urszula,Rózalski, Marek
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p. 3516 - 3521
(2007/10/03)
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- Convenient synthesis of volatile Streptomyces lactones
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A convenient three-step synthetic approach towards 3-alkyl-5-methyl-2[5H] furanones is described. The steps involved in the synthesis are domino primary alcohol oxidation-Wittig reaction, acid-catalysed lactonisation and isomerisation. This synthetic appr
- Amonkar, Chandan P.,Tilve, Santosh G.,Parameswaran
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p. 2341 - 2344
(2007/10/03)
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- 2-Diethoxyphosphoryl-4-nitroalkanoates - Versatile intermediates in the synthesis of α-alkylidene-γ-lactones and lactams
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Michael addition of various nitroalkanes 7a-f to ethyl (2- diethoxyphosphoryl)acrylate (6) gave 2-diethoxyphosphoryl-4-nitroalkanoates 8a-f. Transformation of the nitro functionality into hydroxy or amino group and cyclization yielded 3-(diethoxyphosphory
- B?aszczyk, Edyta,Krawczyk, Henryk,Janecki, Tomasz
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p. 2685 - 2688
(2007/10/03)
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- Methylenelactones syntheses in supercritical fluids
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Alpha-methylenelactone is produced from butyrolactone and valerolactone by the addition of formaldehyde in a supercritical fluid.
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- Carbonylation of alkynols catalyzed by Pd(II)/2-PyPPh2 dissolved in organic solvents and in ionic liquids: A facile entry to α-methylene γ- and δ-lactones
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The carbonylation of terminal 3-alkyn-1-ols and 1-alkyn-4-ols by Pd(OAc)2 associated with 2-(diphenylphosphino)pyridine (2-PyPPh2) dissolved in organic solvents or in 1-n-butyl-3-methyl imidazolium ionic liquids affords quantitatively and selectively exo-α-methylene γ- and δ-lactones, respectively. In the case of the reactions performed in ionic liquids (biphasic conditions), the lactones were isolated by simple distillation and the ionic catalyst solution can be reused.
- Consorti, Crestina S,Ebeling, Gunter,Dupont, Jaírton
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p. 753 - 755
(2007/10/03)
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- Thiophosphates and selenophosphates in organic synthesis. A new approach to exocyclic olefins and bicyclic enones
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Efficient synthesis of α-methylene-cycloalkanones, α-methylene-lactones and α-alkylidene-lactones as well as bicyclic enones were developed using thiophosphates 3, 9, 15 and selenophosphates 4 as key intermediates.
- Skowrońska, Aleksandra,Krawczyk, Ewa,Koprowski, Marek,Dybowski, Piotr
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p. 409 - 412
(2007/10/03)
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- A New Method for the Preparation of α- Methylene-γ-butyrolactones Using 3-Ethoxycarbonyl-3-(phenylsulphonyl)cyclobutanone
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The reaction of 3-ethoxycarbonyl-3-(phenylsulphonyl)cyclobutanone with Grignard reagent or aryllithium gave 1-(alkyl or aryl)-3-ethoxycarbonyl)cyclobutanol which was treated with potassium hydride, reduced with LiBH4 in the presence of ZnCl2, and treated
- Fujiwara, Tooru,Morita, Koichi,Takeda, Takeshi
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p. 1524 - 1527
(2007/10/02)
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- The Stereochemistry of Organometallic Compounds. XXX. Hydrocyanation of Alkynol Ethers: a New Stereospecific Route to α-Alkylidene γ-Lactones
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The regioselectivity of hydrocyanation of a range of protected α- and β-hydroxyalkynes has been investigated and shown to by highly susceptible to steric effects.Some of the products from hydrocyanation of protected β-hydroxyalkynes have been converted into α-alkylidene γ-lactones.
- Jackson, W. Roy,Perlmutter, Patrick,Smallridge, Andrew J.
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p. 251 - 261
(2007/10/02)
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- A New Synthesis of 5-Methyl-3-methylene-γ-butyrolactone
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An useful synthesis of 5-methyl-3-methylene-γ-butyrolactone (6) involving a Wittig-Horner reaction as a key step is described.
- Ravikumar, V. T.,Swaminathan, S.,Rajagopalan, K.
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p. 292 - 293
(2007/10/02)
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- A New Stereospecific Route to α-Alkylidene γ-Lactones
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Hydrocyanation of a range of protected β-hydroxyalkynes gives unsaturated nitriles which can be cyclised to α-alkylidene γ-lactones and in most cases the regioselectivity of hydrocyanation can be controlled giving the desired cyanoalkenes with stereospecific formation of the E-isomer.
- Jackson, W. Roy,Perlmutter, Patrick,Smallridge, Andrew J.
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p. 1509 - 1510
(2007/10/02)
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- Synthesis of 3-Methylenmonosubstituted-2-oxo-tetrahydrofurans from 3-Phosphonolactones
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The synthesis of 3-methylenmonosubstituted-2-oxo-tetrahydrofurans 3a-f from 3-phosphonolactones 1a-b and the aldehyds 2a-d is described. 1H NMR spectra of the 3-methylenmonosubstituted-2-oxo-tetrahydrofurans are discussed. - Keywords: 3-Methylenmonosubstituted-2-oxo-tetrahydrofurans, 1H NMR spectra
- Falsone, Giaocchino,Spur, Bernd,Peters, Wilfried
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p. 493 - 496
(2007/10/02)
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- Palladium-Catalyzed Carbonylation of Vinyl Halides: A Route to the Synthesis of α-Methylene Lactones
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α-Methylene γ-lactones were synthesized in high yields by the palladium-catalyzed carbonylation reactions of alkyl-substituted 3-bromobut-3-en-1-ols under mild conditions.The bromo alcohols were obtained by the reaction of magnesium bromide with various epoxides followed by conversion of the trimethylsilyl group to bromide.By starting with optically active epoxides such as (R)-1,2-epoxypropane or (2R,3R)-2,3-epoxybutane, the corresponding lactones could be obtained virtually optically pure.The carbonylation reaction is selective in that it generates only γ-lactones when there is a choice of two vinylic iodides or two alcohols that could lead either to the five- or six-membered rings.
- Martin, Larry D.,Stille, J. K.
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p. 3630 - 3633
(2007/10/02)
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- USE OF METHYL 3-(N,N-DIMETHYLAMINO)PROPIONATE AS A SYNTHON FOR THE CONSTRUCTION OF α-METHYLENE γ-BUTYROLACTONES
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The lithium enolate of methyl 3-(N,N-dimethylamino)propionate reacts with allylic halides to give alkylation products which may be converted into α-methylene γ-butyrolactones by a reaction sequence which includes iodolactonization among other simple steps.
- Yu, Lin-Chen,Helquist, Paul
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p. 591 - 598
(2007/10/02)
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- β-Amino Ester Enolate as an Acrylate Anion Equivalent for the Synthesis of α-Methylene Esters, Acids, and Lactones
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The lithium enolate (18) of methyl 3-(dimethylamino)propionate (17) has been developed as a synthetic equivalent of the α-anion (15) of acrylic acid.The enolate, obtained by treatment of the free ester (17) with lithium diisopropylamide, may be alkylated with a variety of alkyl halides to give products which may be considered to be protected acrylate esters.Unmasking is accomplished by quaternization with methyl iodide followed by DBN-induced elimination to give the free acrylates.The products derived from allylic halides may conveniently be converted into α-methylene lactones.
- Yu, Lin-Chen,Helquist, Paul
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p. 4536 - 4541
(2007/10/02)
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- GENERAL SYNTHESIS OF EXOMETHYLENE-γ-LACTONES VIA THE RETRO-DIELS-ALDER REACTION
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New synthetic methods of tulipalin A were deviced via the retro-Diels-Alder reaction and the generality was demostrated by the synthesis of several α-methylene-γ-alkyl-γ-butyrolactones.
- Ichihara, Akitami,Nio, Noriki,Sakamura, Sadao
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p. 4467 - 4468
(2007/10/02)
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- Addition of Aldehydes to Activated Double Bonds, XXII. Addition of Aliphatic Aldehydes to α,β-Unsaturated Esters and Nitriles
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Thiazolium salt catalysed addition of aliphatic aldehydes to α,β-unsaturated esters and nitriles leads to γ-ketocarboxylic esters (1-24) and γ-ketonitriles (25-32).
- Stetter, Hermann,Basse, Wolfram,Nienhaus, Juergen
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p. 690 - 698
(2007/10/02)
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- Studies on New Synthetic Pathways to Δα,β-Butenolides from α-Methylbutanolides. II. Electrolytic Oxidation of Simple α-Carboxy-α-methylbutanolides
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A new approach to the synthesis of Δα,β-butenolides from γ-butanolides by means of the electrolytic oxidation of α-carboxy-α,γ-dimethyl-γ-butyrolactone (3b) and its α-carboxy-α-methyl analog (3d) resulted in predominant formation of the endocyc
- Kawamata, Takeshi,Inayama, Seiichi,Sata, Kazuko
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p. 277 - 281
(2007/10/02)
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- Synthesis of α-Methylene-γ-butyrolactones: A Structure-Activity Relationship Study of Their Allergenic Power
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Thirty-five α-methylene-γ-butyrolactones has been prepared and their allergenic properties tested on the skin of guinea pigs experimentally sensitized to (a) alantolactone (1), (b) isoalantolactone (2), and (c) α-methylene-γ-butyrolactone (3).The two firs
- Schlewer, Gilbert,Stampf, Jean-Luc,Benezra, Claude
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p. 1031 - 1038
(2007/10/02)
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