- Novel synthesis routes for the preparation of low toxic vinyl ester and vinyl carbonate monomers
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UV curing of photopolymerizable monomers, like (meth)acrylates, has been utilized for coatings for more than half a century and more recently in further developed areas such as tissue engineering. However, these monomers have major disadvantages, e.g., high irritancy and cytotoxicity, which leads to limited use in tissue engineering regarding health issues. Vinyl esters (VE) and vinyl carbonates (VC) can compete with (meth)acrylates in terms of material properties and have significantly lower toxicity, but lack in cost efficient synthesis methods. The purpose of this communication is to establish new pathways to overcome this drawback. It was shown that VEs can be synthesized either by vinyloxy trimethylsilane or by acetaldehyde in excellent yields. Moreover, a new method to synthesize vinyl chloroformate as precursor for VCs in lab scale was evolved by a catalyzed reaction of vinyloxy trimethylsilane with a phosgene solution. Finally, the cytotoxicity tests showed auspicious results.
- Hofecker, Andreas,Knaack, Patrick,Liska, Robert,Markovic, Marica,Ovsianikov, Aleksandr,Steinbauer, Patrick
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supporting information
p. 3629 - 3641
(2020/10/02)
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- Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II): Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption
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Oxidative ethylene hydrophenylation catalyzed by palladium(II) acetate with Cu(II) oxidants to produce styrene generally suffers from low selectivity and/or low yield. Commonly observed side products include vinyl carboxylates and stilbene. In this Article, the selectivity for styrene formation by Pd(OAc)2 is studied as a function of reaction temperature, ethylene pressure, Br?nsted acid additive, Cu(II) oxidant amount, and oxygen pressure. Under optimized conditions, at high temperatures (180 °C) and low olefin pressure (20 psig), nearly quantitative yield (>95%) of styrene is produced based on the limiting reagent copper(II) pivalate. We propose the selectivity for styrene versus vinyl pivalate at 180 °C is due to a palladium-catalyzed conversion of benzene and in situ formed vinyl pivalate to styrene.
- Jia, Xiaofan,Foley, Aisling M.,Liu, Chang,Vaughan, Benjamin A.,McKeown, Bradley A.,Zhang, Sen,Gunnoe, T. Brent
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supporting information
p. 3532 - 3541
(2019/09/12)
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- PROCESS FOR THE PRODUCTION OF HIGHER CARBOXYLIC ACID VINYL ESTERS
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This invention concerns a process for the production of vinyl esters of carboxylic acids with 3 to 20 carbon atoms, via vinylation in the presence of palladium (Pd) catalyst in combination with copper (Cu) as co-catalyst stabilized by organic salts in the presence of ethylene and air or oxygen.
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Page/Page column 40; 42-43
(2017/01/31)
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- Method for Producing Vinyl Esters
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The present invention relates to a continuous, catalytic process for preparing a vinyl ester of the formula R—C(O)O—CH═CH2 by reaction of a carboxylic acid of the formula R—C(O)OH with a transvinylating reagent of the formula R1—C(O)O—CH═CH2, wherein the reaction is effected at a temperature of 90 to 160° C. and at a pressure of 0.5 to 15 MPa without withdrawal of a reactant in the presence of a transition metal catalyst containing at least one transition metal from the group of ruthenium, osmium, rhodium, iridium, palladium and platinum, and then the resulting reaction mixture is separated into its constituents.
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Paragraph 0050
(2014/12/09)
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- Transvinylation as a First Stage of Coupling Production of Vinyl Esters and Acetic Acid or Propionic Acid Reaction Products
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Process for coproduction of a vinyl ester of the formula R—C(O)O—CH═CH by transvinylation reaction of a carboxylic acid of the formula R—C(O)OH with a transvinylating reagent of the formula R1—C(O)O CH═CH2, characterized in that (a) the transvinylation reaction is conducted continuously at a temperature of 90 to 160° C. and at a pressure of 0.5 to 15 MPa without withdrawal of a reactant in the presence of a transition meta/catalyst containing at least one transition metal selected from the group of ruthenium, osmium, rhodium, iridium, palladium and platinum; (b) the resulting reaction mixture is separated into its constituents and the vinyl ester of the formula R—C(O)O—CH═CH2 and the carboxylic acid of the formula R1—C(O)—OH are removed; and (c) the carboxylic acid obtained after step (b) is converted to a derivative of the formula R1—C(O)—X, R1—CH2—OH or R6—C(O)—OH in which X is vinyloxy, O—CH—CH2, halogen, alkoxy of the formula OR2 in which R2 is a substituted or unsubstituted hydrocarbyl radical having 1 to 10 carbon atoms, amino of the formula NR3R4 in which R3 and R4 are each independently hydrogen or a substituted or unsubstituted hydrocarbyl radical having 1 to 10 carbon atoms, or carboxyl of the formula O—C(O)—R5 in which R5 is hydrogen or a substituted or unsubstituted hydrocarbyl radical having 1 to 10 carbon atoms, and R6 is the partly or fully halogen-substituted R1 radical.
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Paragraph 0058-0059
(2014/12/09)
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- Ethenolate transfer reactions: A facile synthesis of vinyl esters
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A simple and efficient metal-free ethenolate transfer reaction has been elaborated in moderate-to-high yields from vinyl acetate. This reaction was accomplished by generation of potassium ethenolate, which was then reacted with homo and mixed anhydrides of aliphatic, aryl and heteroaryl acids, to yield the corresponding vinyl esters. The utility of thus generated vinyl esters was then probed by carrying out intramolecular Heck reactions to give isobenzofuran-1(3H)-one derivatives in excellent yields. Copyright
- Appaye, Srinivasan Kaliyaperumal,Nikumbh, Satish Pandurang,Govindapur, Rajeshwar Reddy,Banerjee, Shyamapada,Bhalerao, Dinesh S.,Kumar, Unniaran K. Syam
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p. 1115 - 1122
(2014/09/17)
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- VINYL ESTER PRODUCTION FROM ACETYLENE AND CARBOXYLIC UTILIZING HOMOGENEOUS CATALYST
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A process for the selective production of vinyl ester by the reaction of a carboxylic acid with acetylene with a homogeneous catalyst is disclosed and claimed. In a preferred embodiment of this invention, reaction of benzoic acid and acetylene in the presence of Group VIII metal complex catalyst at a temperature of about 50 to 1800C results in quantitative yields of vinyl benzoate.
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Page/Page column 68-69
(2010/11/18)
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- Process for Preparing Vinyl Carboxylates
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The present invention relates to a process for preparing vinyl carboxylates, wherein a carboxylic acid is reacted with an alkyne compound in the presence of a catalyst which is selected from carbonyl complexes, halides and oxides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of ≦300° C. The process gives the desired vinyl esters with high yield.
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Page/Page column 6
(2009/01/24)
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- Synthesis of higher vinyl esters from ethylene and higher carboxylic acids
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A homogeneous liquid phase process for producing a vinyl carboxylate in which the carboxylate group contains at least four carbon atoms, which process comprises (1) forming a homogeneous liquid reaction mixture containing ethylene, oxygen carboxylic acid having at least three carbon atoms, a palladium (II) catalyst and a copper (II) oxidant and (2) maintaining the reaction mixture under conditions at which the ethylene and the carboxylic acid react to form the vinyl carboxylate in the homogeneous liquid reaction mixture, with the proviso that at least one of the following conditions exists during said process: (i) the copper (II) oxidant is a copper (II) carboxylate in which carboxylate group has a molecular weight that is higher than the molecular weight of the carboxylate group in the carboxylic acid; (ii) the palladium (II) catalyst is formed in situ in the reaction mixture by the oxidation of a palladium (0) colloid; and/or (iii) the reaction mixture also contains a polyglyme compound as a promoter.
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- Acyl Transfer Reactions in the Gas Phase. Ion-Molecule Chemistry of Vinyl Acetate
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An ion cyclotron resonance study of the ion-molecule reactions of vinyl acetate with methanol in the gas phase has revealed the formation of structurally different ions having the composition of protonated vinyl acetate.Deuterium-labeled reactants (CD3CO2CH=CH2 with CH3OH or CD3OD) gave product ions showing incorporation of up to two deuteriums in the vinyl group, indicating coexistence and interconversion of O-protonated and C-protonated vinyl acetate.Evidence was also obtained for a third MH+ ion for which the proposed structure is protonated 3-oxobutanal.This ion is believed to be formed by attack of CH3CO+ at the terminal vinylic carbon with loss of the ester acyl group as ketene.The ion reacts with methanol to give m/z 101 by loss of water.In contrast, protonated vinyl acetate reacts with methanol by an acyl transfer process to give (AcOCH3)H+, m/z 75.The related ion chemistry of vinyl propanoate, vinyl 2,2-dimethylpropanoate, and isopropenyl acetate is also described.Each of the acyl transfer reactions observed is consistent with formation of intermediate acylium ion complexes rather than tetracovalent addition complexes.Attempts were made to generate tetracovalent intermediates by an independent route from ortho esters of vinyl acetate.Dissociation of the ortho ester CH3C(OCH=CH2)2(OCH3) to dioxacarbocations was the dominant reaction, but the product ions were unreactive with H2O, CH3OH, or t-C4H9OH.The mechanistic implications of these results are discussed.
- Kim, Jhong K.,Caserio, Marjorie C.
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p. 4624 - 4629
(2007/10/02)
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