cas 542-10-9, Ethylidene diacetate | Articles data

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NEW TRANSFORMATIONS OF VINYL ACETATE UNDER THE INFLUENCE OF THE COMPLEX Rh(PPh3)3Cl
The strictly regioselective hydrocarboxylation of vinyl acetate to ethylidene diacetate by acetic acid formed in situ from vinyl acetate was realized for the first time with Rh(PPh3)3Cl as catalyst.The transformation of vinyl acetate into benzene, acetophenone, and acetylene was also realized. Keywords: Hydrocarboxylation, vinyl acetate, metal complex catalyst.
Dzhemilev, U. M.,Khusnutdinov, R. I.,Shchadneva, N. A.
p. 1100 - 1101
(1992)
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Acetic acid methyl ester synthesis method for synthesizing double-acetic acid carbonate
The invention relates to a synthesis method of ethylidene diacetate from methyl acetate, which mainly solves the problems of low conversion rate of methyl acetate and low selectivity of ethylidene diacetate in the prior art. MeOAc, CO and H2 used as raw materials react in the presence of a catalyst by mainly using SOCl2 or SOCl2-sulfolane mixture as a solvent to generate the ethylidene diacetate. The catalyst comprises a main catalyst, a cocatalyst and an accelerator, wherein the main catalyst adopts VIII metals or compounds thereof, the cocatalyst is a halogen-containing compound, and the accelerator is a nitrogen oxygen organic matter or phosphorus-containing compound. The technical scheme well solves the problems, and can be used for producing vinyl acetate.
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Paragraph 0047; 0048; 0049

(2017/01/12)

Method for synthesizing vinyl acetate through methyl acetate carbonylation
The invention relates to a method for synthesizing vinyl acetate through methyl acetate carbonylation. When vinyl acetate is prepared from methyl acetate through the route of carbonylation and cracking, vinyl acetate yield and selectivity are low. The invention mainly aims at solving the problems. The method comprises the following steps: methyl acetate carbonylation is carried out, such that ethylene diacetate is obtained; and ethylene diacetate is cracked, such that vinyl acetate is obtained. A carbonylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and has active components comprising at least one selected from iron-series elements, at least one selected from metalloid elements and at least one metal element selected from IB and alkaline earth metals. With the technical scheme, the technical problem is well solved. The method can be used in industrial production of vinyl acetate.
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Paragraph 0166; 0167; 0168; 0169; 0170; 0171

(2016/12/16)

ZSM-5-SO3H as a novel, efficient, and reusable catalyst for the chemoselective synthesis and deprotection of 1,1-diacetates under eco-friendly conditions
ZSM-5 has been modified as supported sulfuric acid (ZSM-5-SO3H) and introduced for the first time as a mild, convenient, reusable, and heterogeneous catalyst. Various types of aldehydes were efficiently converted to their 1,1-diacetates using a catalytic amount of ZSM-5- SO3H in excellent yields under solvent-free and heterogeneous conditions at room temperature. The deprotection of 1,1-diacetates has also been achieved using this novel catalyst in ethanol. The procedure is operationally simple, environmentally benign, and only a stoichiometric amount of anhydride is used. Springer-Verlag 2011.
Massah, Ahmad Reza,Kalbasi, Roozbeh Javad,Shafiei, Anahita
experimental part
p. 643 - 652
(2012/07/14)

Preparation of acetic acid
The disclosure relates to a process for the preparation of acetic acid. The process comprises reacting a decanter heavy, organic phase of an acetic acid production process with acetic anhydride to convert acetaldehyde in the decanter heavy, organic phase to ethylidene diacetate and separating it from the decanter heavy, organic phase. Ethylidene diacetate can be hydrolyzed to recover acetic acid.
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(2011/10/19)

Hydroacetoxylation of olefins with acetic acid genetated in situ from vinyl acetate in the presence of ruthenium complexes
Ruthenium complexes catalyze the decomposition of vinyl acetate releasing the acetic acid and its subsequent addition to linear and cyclic olefins.
Khusnutdinov,Shchadneva,Khisamova,Dzhemilev
body text
p. 155 - 160
(2011/05/03)

Integrated process for the production of vinyl acetate from acetic acid via acetaldehyde
This invention provides an integrated multistep economical process for the production of vinyl acetate monomer (VAM) from acetic acid in the vapor phase. First, acetic acid is selectively hydrogenated over a hydrogenating catalyst composition to form acetaldehyde. Acetaldehyde so formed can be converted to ethylidene diacetate via reaction with acetic anhydride. In a subsequent step so formed ethylidene diacetate is thermally decomposed to form VAM and acetic acid. Alternatively, acetaldehyde formed in the first step can selectively be reacted with ketene to form VAM. In an embodiment of this invention reaction of acetic acid and hydrogen over platinum and iron supported on silica selectively produces acetaldehyde in a vapor phase at a temperature of about 300° C., which is selectively hydrogenated over platinum supported catalyst to form ethanol and dehydrated over NAFION catalyst to form ethylene at a temperature of about 185° C., which is mixed with molecular oxygen, acetic acid and reacted over a palladium/gold/potassium catalyst supported on titania to form VAM at a temperature of about 150° C. to 170° C.
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(2010/07/08)

CARBONYLATION PROCESS
Disclosed is an improved carbonylation process for the production of carboxylic acids, carboxylic acid esters, and/or carboxylic acid anhydrides wherein a carbonylation feedstock compound selected from one or more organic oxygenates such as alcohols, ethers, and esters is contacted with carbon monoxide in the presence of a carbonylation catalyst and one or more onium compounds. The carbonylation process differs from known carbonylation processes in that a halide compound, other than the onium salt, such as a hydrogen halide (typically, hydrogen iodide) and/or an alkyl halide (typically, methyl iodide), extraneous or exogenous to the carbonylation process is not fed or supplied to the process. The process can be improved by using a bidentate ligand comprising two functional groups selected from tertiary amines and tertiary phosphines, such as 2,2′-bipyridine and diphosphine derivatives.
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(2009/10/06)

CARBONYLATION PROCESS
Disclosed is a carbonylation process for the production of carboxylic acids, carboxylic acid esters and/or carboxylic acid anhydrides wherein a carbonylation feedstock compound selected from one or more organic oxygenates such as alcohols, ethers, and esters is contacted with carbon monoxide in the presence of a carbonylation catalyst and one or more onium compounds. The carbonylation process differs from known carbonylation processes in that a halide compound such as a hydrogen halide, typically hydrogen iodide, and/or alkyl halide, typically methyl iodide, extraneous or exogenous to the carbonylation process is not fed or supplied separately to the process.
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(2008/06/13)

An efficient method for the synthesis of acylals from aldehydes using silica-supported perchloric acid (HClO4-SiO2)
The synthesis of acylals from structurally diverse aldehydes has been performed in excellent yields under solvent-free conditions using HClO4-SiO2 as a mild, convenient, reusable, and heterogeneous catalyst. The procedure is operationally simple, environmentally benign and has the advantage of enhanced atom utilization. Furthermore, the catalyst can be recovered simply and reused efficiently a number of times without appreciable loss of activity.
Kamble, Vinod T.,Jamode, Vasant S.,Joshi, Neeta S.,Biradar, Ankush V.,Deshmukh, Rameshchandra Y.
p. 5573 - 5576
(2007/10/03)

Indium tribromide as a highly efficient and versatile catalyst for chemoselective synthesis of acylals from aldehydes under solvent-free conditions
A mild and efficient method has been developed for the chemoselective preparation of acylals from aldehydes in the presence of catalytic amounts (0.01-1.0 mol%) of InBr3 under solvent-free conditions in very good to excellent yields.
Yin, Liang,Zhang, Zhan-Hui,Wang, Yong-Mei,Pang, Mei-Li
p. 1727 - 1730
(2007/10/03)

A rapid and convenient synthesis of 1,1-diacetates from aldehydes and acetic anhydride catalyzed by PVC-FeCl3 catalyst
A variety of aldehydes can be converted into 1,1-diacetates rapidly and conveniently in the presence of catalytic amounts of poly(vinyl chloride) supported ferric chloride reagent at room temperature in excellent yields.
Li
p. 3913 - 3917
(2007/10/03)

The chemistry of acylals. 3. Cyanohydrin esters from acylals with cyanide reagents
(equation presented) When treated with KCN in DMSO at room temperature, acylals from aliphatic aldehydes gave the corresponding cyanohydrin esters in good to excellent yields. Acylals from aromatic aldehydes were less reactive and gave several byproducts in addition to fair yields of cyanohydrin under the same conditions. Trimethylsilyl cyanide mixed with titanium(IV) chloride afforded cyanohydrin esters in good to excellent yields from both aliphatic and aromatic aldehydes.
Sandberg, Marcel,Sydnes, Leiv K.
p. 687 - 689
(2007/10/03)

Electrophilic reactions of carboyl compounds and derivatives thereof: XIII preparation of bifunctional compounds from aldehydes and olefins by acylation under acidic catalysis
The reactions of aldehydes and their O-acylated derivatives (α-chloroesters, acylals) with olefins and α-ethoxystyrene in the presence of SnCl4 and ZnCl2 were investigated. The reactions afforded various bifunctional derivatives: diols, hydroxyesters, chloroesters, 1,3-ketoalcohols.
Luk'yanov,Koblik,Murad'yan
p. 1593 - 1599
(2007/10/03)

Selectivity Behavior in Hydrocarbonylation of Methyl Acetate Using Homogeneous Rh Complex Catalyst
Hydrocarbonylation of methyl acetate using various homogeneous transition metal complex catalysts has been studied.It was observed that Rh(CO)Cl(PPh3)2 was the most active and selective catalyst for ethylidene diacetate synthesis.The effect of the catalyst, methyl acetate, and methyl iodide concentrations; temperature; and partial pressures of CO, H2, and various transition metal complexes as co-catalysts on the selectivity behavior has been studied.Palladium complexes were found to enhance the selectivity of ethylidene diacetate substantially.Catalyst concentration, partial pressures of CO and H2, and temperature also influence the selectivity pattern substantially.On the basis of these results, a possible reaction mechanism is discussed.
Kelkar, A. A.,Chaudhari, R. V.
p. 334 - 343
(2007/10/03)

Vinylation and acylation of adamantane by vinyl acetate through the action of rhodium complexes
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Khusnutdinov,Shchadneva,Dzhemilev
p. 2527 - 2527
(2007/10/02)

Production of ethylidene diacetate from dimethyl acetal
A process for the production of ethylidene diacetate by the catalytic reaction of dimethyl acetal, methyl acetate and carbon monoxide in contact with a homogeneous catalyst system containing rhodium metal atom and lithium iodide.
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(2008/06/13)

The Synthesis of 1-Aminoalkylphosphonic Acids. A Revised Mechanism of the Reaction of Phosphorus Trichloride, Amides and Aldehydes or Ketones in Acetic Acid (Oleksyszyn Reaction)
The mechanism of the amidoalkylation of trivalent phosphorus compounds in acetic acid has been reinvestigated.Evidence is presented that 1-(acylamino)alkyl acetates 5 and not N,N'-alkylidenebisamides 2 are the intermediates in this reaction.Supporting literature analogies are discussed.This paper also describes a convenient procedure for the preparation of crude (acylamino)alkyl alkanoates 5, which are excellent amidoalkylating agents.The usefulness of these reagents is demonstrated by a simple two-step "one pot" synthesis of 1-aminoalkylphosphinic acids 1.
Soroka, Miroslaw
p. 331 - 334
(2007/10/02)

Process for producing vinyl acetate
A process for producing vinyl acetate which comprises reacting acetic anhydride with hydrogen in the presence of a catalyst comprising (a) a metal belonging to Group VIII of the Periodic Table or a compound of the metal, and (b) (i) an acidic substance, or (ii) a halide is disclosed.
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(2008/06/13)

Neuartige basische Liganden fuer die homogenkatalytische Methanolcarbonylierung XXIX. Kieselgelfixierte (Ether-Phosphan)Rhodium-Komplexe in der katalytischen Hydrocarbonylierung von Methylacetat zu Ethylidendiacetat
The heterogenized (ether-phosphane)rhodium complexes 2Rh(CO)Cl (2a-d) are obtained from the silica anchored silylalkyl(ether-phosphanes) 1a-d and (μ-CIRh(CO)2>2.The palladium complex 2PdCl2 (4) is formed by addition of (COD)PdCl2 to the heterogenized alkyldiphenylphosphane (3).High pressure experiments provide information on conversion and selectivity in the hydrocarbonylation of methylacetate to ethylidenediacetate, if parameters like pressure, temperature, ether moieties in the ligands 1a-d, and composition of catalyst and synthesis gas are varied.To investigate the influence of temperature and pressure on the leaching of metals, the supported catalysts are recovered and re-used. trans-(PO)2Rh(CO)Cl (7e) is formed in homogeneous phase by reaction of 2 (5) with the ligand 6e O = Me3Si(CH2)3P(Ph)CH2CH2OCH3>.Oxidative addition of CH3I to 7e affords trans-(PO)2Rh(CO)(CH3)(I)2 (9e).In the presence of CO methyl migration in 9e leads to trans-(PO)2Rh(CO)(COCH3)(I)2 (10e).Reductive elimination of CH3C(O)I from 10e regenerates 7e, probably via the cationic intermediate O)-(P O)Rh(CO)COCH3)I> (8e).The unstable cationic (ether-phosphane)rhodium complex O)(P O)Rh(CO)COCH3)I> (11e) which is isostructural to 8e is obtained by I- abstraction from 10e.
Lindner, Ekkehard,Glaser, Erhard,Mayer, Hermann August,Wagner, Peter
p. 325 - 337
(2007/10/02)

Thermolysis of 2-acyloxy-Δ3-1,3,4-oxadiazolines. Evidence for a preferred sense of cycloreversion to carbonyl ylides and for fast 1,4-sigmatropic ylide rearrangement
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Majchrzak,Warkentin
p. 1753 - 1759
(2007/10/02)

Aldehydes via Palladium Catalysed Reductive Carbonylation of Esters
Aldehydes are obtained in high selectively via the low pressure, palladium catalysed reaction of esters and synthesis gas (CO-H2).
Graff, James L.,Romanelli, Michael G.
p. 337 - 338
(2007/10/02)

Process for making acetic anhydride
The disclosure relates to a process for making acetic anhydride wherein methyl acetate and/or dimethylether (is) are reacted with carbon monoxide under practically anhydrous conditions at temperatures of 390° to 540° K., under pressures of 1 to 300 bars in the presence of a catalyst system comprised of noble metals belonging to group VIII of the Periodic System of the elements or their compounds, iodine and/or its compounds and a tertiary or quaternary organic nitrogen, phosphorus, arsenic or antimony compound. More particularly, use is made of a catalyst system containing vanadium or niobium or their compounds as additional constituents, the catalyst system being used in combination with reaction gas containing carbon monoxide and 5 to 30 volume % hydrogen.
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(2008/06/13)

MECHANISM OF THE SYNTHESIS OF VINYL ACETATE AND 1,1-DIACETOXYETHANE FROM ACETYLENE IN SOLUTIONS OF MERCURY(II) ACETATE
The preparative and kinetic relationships governing the hydroacetylation of acetylene in the Hg(OAc)2-AcOH-p-CH3C6H4SO3H system at 85 deg C were investigated.A mechanism is proposed, according to which the vinyl acetate and 1,1-diacetoxyethane are formed in two parallel paths.
Alekseeva, N. F.,Chalova, Z. I.,Temkin, O. N.
p. 431 - 435
(2007/10/02)

Electrogenerated Bases. VI. Reaction of Electrogenerated Superoxide with Some Carbon Acids. II.
Electrogenerated superoxide and molecular oxygen were allowed to react sequentially with a number of esters, nitriles, N,N-dialkylamides, sulfones, and aliphatic nitro compounds.The α-methyl groups in these compounds bore aliphatic and/or aromatic substituents.When the electron-withdrawing group (EWG) of these carbon acids could be displaced intact (nitile 2, ArSO2 4, nitro) good to excellent yields of the corresponding carbonyl compounds could be obtained.The efficiency of the transformation depended upon the nature of the substituents: α,α-diphenyl (e.g., 2a) > α-methyl-α-phenyl (2b) > α,α-dimethyl.By conducting the electrolysis in the presence of acetic anhydride it was shown that the known conversion of phenylacetonitrile (2d) to benzoic acid did indeed proceed via benzaldehyde.When the EWG itself could be cleaved (esters 1, N,N-dialkyl-amides 3), this methodology produced α-hydroxylated compounds and the products resulting from fragmentation of the EWG and also from its complete displacement.The effects of the α-substituents were similar to those above.
Sugawara, M.,Baizer, M. M.,Monte, W. T.,Little, R. D.,Hess, U.
p. 509 - 518
(2007/10/02)

ELECTROGENERATED BASES VII. NOVEL SYNTHESES OF ETHYL GLYOXALATE AND DIETHYL KETOMALONATE VIA ELECTROGENERATED SUPEROXIDE
Using electrogenerated tetraalkylammonium superoxide plus oxygen ethyl cyanoacetate has been converted (a) directly to ethyl glyoxylate and (b) in a "one-pot" two-step synthesis to the oxomalonate.
Sugawara, M.,Baizer, M. M.
p. 2223 - 2226
(2007/10/02)

Catalysis by Solid Superacids; 16. Improved Nafion-H Catalyzed Preparation of 1,1-Diacetates from Aldehydes
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Olah, George A.,Mehrotra, Ashok K.
p. 962 - 963
(2007/10/02)

SYNTHESIS AND SOME TRANSFORMATIONS OF VINYL β-ACETYL- AND β-BENZOYLACRYLATES
Vinyl β-acetyl- and β-benzoylacrylates were obtained by transvinylation with vinyl acetate in the presence of the catalyst Hg(OCOCH3)2.BF3.O(C2H5)2.It was shown that the reactions with bromine, mercuric acetates, and butyl hydrosulfide at the vinyloxy group are regioselective.
Komarova, L. I.,Zhuravlev, S. V.,Sal'nikova, L. V.
p. 1422 - 1425
(2007/10/02)

Vicinal Glycol Esters from Synthesis Gas
Vicinal glycol esters, such as ethylene glycol acetate esters, are prepared from synthesis gas via the use of homogeneous ruthenium catalysis.
Knifton, John F.
p. 188 - 189
(2007/10/02)

Phosphorus Trichloride as Catalyst in the Preparation of 1,1-Diacetates from Aldehydes
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Michie, Jacqueline K.,Miller, J. Allen
p. 824
(2007/10/02)

HOMOGENEOUS-CATALYTIC REACTIONS OF ALKENES. III. REFINEMENT OF THE MECHANISM OF DECOMPOSITION OF ORGANIC ? COMPLEX OF PALLADIUM
The homogeneous-catalytic oxidation of ethylene in acetic acid leads to the formation of an organopalladium ?-complex , which dissociates into ethylene glycol monoacetate, vinyl acetate, and ethylidene diacetate, depending on the nature of the ligands.The various mechanisms for the decomposition of the ? complex are due to the effective positive charge at the palladium atom; the greater the charge, the more likely is migration of the hydride ion to the addend from the β-carbon atom or isomerization of the complex into the α-ethoxyethyl compound and, accordingly, the higher the yield of vinyl acetate and ethylidene diacetate.Increase in the electron density at the palladium atom leads to decomposition of the organometallic ? complex to the ethylene glycol monoacetate in the presence of water molecules.
Devekki, A. V.,Mushenko, D. V.,Fedorov, V. S.
p. 2250 - 2254
(2007/10/02)

Catalytic process for the conversion of ethyl benzene to equimolar amounts of vinyl acetate and phenol
Equimolar amounts of vinyl acetate and phenol may be prepared by oxidation of ethyl benzene. The catalytic oxidation, of ethyl benzene, when carried out in the presence of acetic anhydride, forms phenyl acetate and ethylidene diacetate. Pyrolysis of these two intermediates yields vinyl acetate and phenol. In a further embodiment of this invention it has been found that persulfate promoters such as potassium persulfate, persulfuric acid, or Caro's dry acid are particularly effective promoters for this oxidation reaction.
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(2008/06/13)

HOMOGENEOUS-CATALYTIC REACTIONS OF ALKENES. INVESTIGATION OF THE MECHANISM OF ACETOXYLATION OF ETHYLENE
The formation of ethylene glycol monoacetate in acetic acid containing PdCl4(2-) ions takes place through catalytic acetoxylation of ethylene.A binuclear ? complex of the olefin and palladium is formed preferentially in the initial chemical event and then isomerizes under the influence of the nucleophile (O2, ONO-) to a ?-organometallic compound.In the latter the Pd-C bond undergoes heterolytic cleavage, and the final product is formed with the participation of water molecules.The ethylene glycol and its diacetate obtained in the reaction are the products from secondary transformations of ethylene glycol monoacetate.Acyloxylation a lso occurs when other alkenes and carboxylic acids are used.The reduction in the rate and the cessation of the oxidation of the olefins are due accordingly to the screening of the coordination sphere of palladium in the intermediate compounds by the glycol esters with subsequent displacement of the alkene from the ? complex.
Devekki, A. V.,Koshelev, Yu. N.,Mushenko, D. V.
p. 2148 - 2154
(2007/10/02)

Preparation of diesters
Carboxylic acid anhydrides are contacted with hydrogen in the presence of an insoluble metal hydrogenation catalyst and strong protonic acid to produce 1,1-diesters.
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(2008/06/13)