cas 769-78-8, VINYL BENZOATE | Articles data

Articles about 769-78-8Total 29 be found

Article title
Article abstract
Author
Journal number and time
Download

Novel synthesis routes for the preparation of low toxic vinyl ester and vinyl carbonate monomers
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
supporting information
p. 3629 - 3641
(2020/10/02)

Normal Alpha Olefin Synthesis Using Dehydroformylation or Dehydroxymethylation
The present invention discloses processes for producing normal alpha olefins, such as 1-hexene, 1-octene, 1-decene, and 1-dodecene in a multistep synthesis scheme from another normal alpha olefin. Also disclosed are reactions for converting aldehydes, primary alcohols, and terminal vicinal diols into normal alpha olefins.
-
Paragraph 0127; 0128; 0129

(2019/09/06)

Oxidative Dehydroxymethylation of Alcohols to Produce Olefins
Catalyst compositions for the conversion of aldehyde compounds and primary alcohol compounds to olefins are disclosed herein. Reactions include oxidative dehydroxymethylation processes and oxidative dehydroformylation methods, which are beneficially conducted in the presence of a sacrificial acceptor of H2 gas, such as N,N-dimethylacrylamide.
-
Paragraph 0057; 0058

(2019/09/06)

Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II): Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption
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
supporting information
p. 3532 - 3541
(2019/09/12)

Eco-environmental synthesis of vinyl benzoate through transesterification catalyzed by Pd/C catalyst
The synthesis of vinyl benzoate via transesterification of vinyl acetate with benzoic acid was investigated by a carbon-supported palladium catalyst. The results showed that Pd (5 wt %)/C catalyst presented good catalytic and reusable performance instead of mercuric salts of strong acids. The conditions of the transesterification reaction for achieving high yields of vinyl benzoate were explored. The optimized conditions are as follows: reaction temperature, 80°C, reaction time, 10 h, catalyst dosage, 4.0 wt % of reactants, and benzoic acid/vinyl acetate molar ratio, 1:11, respectively, and the yield of vinyl benzoate was 85.7% with the purity of 98.3%. Meanwhile, the prepared Pd/C catalyst could be recycled five times without significant decrease in activity after separating from the product mixture, and the vinyl benzoate yield is still more than 81%. Furthermore, the eco-environmental synthetic method offers great potential for the industrial scale synthesis of vinyl benzoate.
Gao, Jun,Guan, Dongrui,Xu, Dongmei,Zhao, Liwen,Zhang, Lianzheng,Li, Min
p. 351 - 359
(2018/09/06)

Reusable rhodium catalyst for the selective transvinylation of sp2-C linked carboxylic acid
The vinyl benzoate derivatives were successfully synthesized by the transvinylation reactions that vinyl group transferred from vinyl acetate to aromatic carboxylic acids with the recoverable catalyst RhCl3·3H2O. This catalyst features air stable and tolerance of water, good reusable ability, meanwhile, shows high selectivity for aromatic carboxylic acid in the presence of phenolic hydroxyl. With this method, a variety of vinyl benzoate derivatives can be produced with up to 95% yield.
Jiang, Ruihang,Chen, Zhangpei,Zhan, Kun,Liu, Lei,Zhou, Junjie,Ai, Yongjian,Li, Shuang,Bao, Hongjie,Hu, Ze'nan,Qi, Li,Wang, Jingting,Sun, Hong-bin
supporting information
p. 3279 - 3282
(2018/07/21)

Regio- and Stereoselective Chan-Lam-Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines
Efficient and scalable Cu(II)-mediated enol esterification methodology of carboxylic acids from alkenyl boroxines and boronic acids is presented. The reaction shows a wide scope in aliphatic and aromatic carboxylic acids in combination with several alkenyl boroxines. In the case of 2-substituted alkenyl boroxines the double bond configuration was fully retained in the enol ester product. Also N-hydroxyimides and imides could be transformed in the respective amidooxy vinyl enol ethers and vinyl enamides. Finally, with the exception of methionine, all other 19 canonical amino acids showed their compatibility to give the enol esters in a stereoselective fashion. (Figure presented.).
Steemers, Luuk,Wijsman, Linda,van Maarseveen, Jan H.
supporting information
p. 4241 - 4245
(2018/10/02)

Tandem Catalysis: Transforming Alcohols to Alkenes by Oxidative Dehydroxymethylation
We report a Rh-catalyst for accessing olefins from primary alcohols by a C-C bond cleavage that results in dehomologation. This functional group interconversion proceeds by an oxidation-dehydroformylation enabled by N,N-dimethylacrylamide as a sacrificial acceptor of hydrogen gas. Alcohols with diverse functionality and structure undergo oxidative dehydroxymethylation to access the corresponding olefins. Our catalyst protocol enables a two-step semisynthesis of (+)-yohimbenone and dehomologation of feedstock olefins.
Wu, Xuesong,Cruz, Faben A.,Lu, Alexander,Dong, Vy M.
supporting information
p. 10126 - 10130
(2018/08/23)

Method for synthesizing vinyl carboxylate
The present invention relates to a method for synthesizing carboxylic acid enol esters, in particular to a method for synthesizing vinyl carboxylate. The vinyl carboxylate is prepared by performing asynergistic reaction on a 1-chloroethyl carboxylate represented by a formula 1 and an epoxy compound under the effect of a metal chloride catalyst. In 1-chloroethyl carboxylate represented by the formula 1, n is a natural number larger than or equal to 1, when n=1, the 1-chloroethyl carboxylate includes monocarboxylates in which R represents a hydrocarbon group or a hetero-hydrocarbon group containing carbonyl, an ether bond, a thioether bond, an ester bond, or a peptide bond, and when n is equal to or larger than 2, the 1-chloroethyl carboxylate ester includes di(1-chloroethyl) oxalate and polycarboxylates in which R is a hydrocarbon group or a hetero-hydrocarbon group containing carbonyl, an ether bond, a thioether bond, an ester bond and a peptide bond. Compared with a vinyl acetate exchange method, the synergic method has a lower cost, and the process design is simple and suitable for industrial production. The vinyl carboxylate has a wide range of uses in the field of polymer synthesis and coatings.
-
Paragraph 0045; 0046

(2018/04/26)

Dehalogenation of vicinal dihalo compounds by 1,1′-bis(trimethylsilyl)-1: H,1′ H-4,4′-bipyridinylidene for giving alkenes and alkynes in a salt-free manner
We report a transition metal-free dehalogenation of vicinal dihalo compounds by 1,1′-bis(trimethylsilyl)-1H,1′H-4,4′-bipyridinylidene (1) under mild conditions, in which trimethylsilyl halide and 4,4′-bipyridine were generated as byproducts. The synthetic protocol for this dehalogenation reaction was effective for a wide scope of dibromo compounds as substrates while keeping the various functional groups intact. Furthermore, the reduction of vicinal dichloro alkanes and vicinal dibromo alkenes also proceeded in a salt-free manner to afford the corresponding alkenes and alkynes.
Rej, Supriya,Pramanik, Suman,Tsurugi, Hayato,Mashima, Kazushi
supporting information
p. 13157 - 13160
(2017/12/26)

PROCESS FOR THE PRODUCTION OF HIGHER CARBOXYLIC ACID VINYL ESTERS
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.
-
Page/Page column 40; 42

(2017/01/31)

Method for Producing Vinyl Esters
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.
-
Paragraph 0050

(2014/12/09)

Transvinylation as a First Stage of Coupling Production of Vinyl Esters and Acetic Acid or Propionic Acid Reaction Products
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.
-
Paragraph 0058-0059

(2014/12/09)

Ethenolate transfer reactions: A facile synthesis of vinyl esters
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
p. 1115 - 1122
(2014/09/17)

Process for the semi-continuous transvinylation of carboxylic acids with vinyl acetate
A semi-continuous process is provided for selective formation of a vinyl ester by reactive distillation from a corresponding carboxylic acid. Carboxylic acid, vinyl acetate, and a palladium acetate—bidentate ligand catalyst complex are provided and reacted in a typical embodiment. Acetic acid and vinyl acetate are continuously removed from the reaction mixture and vinyl acetate is recycled to the reaction mixture. The vinyl ester product is separated from the vinyl acetate, residual carboxylic acid, residual acetic acid, and catalyst.
-
Page/Page column 8-9

(2011/11/13)

VINYL ESTER PRODUCTION FROM ACETYLENE AND CARBOXYLIC ACID UTILIZING HETEROGENEOUS CATALYST
A process for the selective production of vinyl ester by the reaction of a carboxylic acid with acetylene under heterogeneous catalytic conditions is disclosed and claimed. In a preferred embodiment of this invention, reaction of benzoic acid and acetylene in the presence of supported platinum catalyst at a temperature of from about 100 to 180°C results in quantitative yields of vinyl benzoate.
-
Page/Page column 33-34

(2010/11/18)

VINYL ESTER PRODUCTION FROM ACETYLENE AND CARBOXYLIC UTILIZING HOMOGENEOUS CATALYST
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.
-
Page/Page column 40-41

(2010/11/18)

Process for Preparing Vinyl Carboxylates
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.
-
Page/Page column 5

(2009/01/24)

Au(I) complexes-catalyzed transfer vinylation of alcohols and carboxylic acids
Au(I) complexes-catalyzed transfer vinylation of alcohols and carboxylic acids has been achieved. The catalyst system consists of 2 mol % AuClPPh3 and 2 mol % AgOAc. Primary alcohols and secondary alcohols were converted into corresponding vinyl ethers in good yield (64-93%); however, tertiary alcohols showed poor reactivities. Carboxylic acids were also transformed into corresponding vinyl esters in good yield (78-96%).
Nakamura, Aki,Tokunaga, Makoto
p. 3729 - 3732
(2008/09/20)

Synthesis of enol and vinyl esters catalyzed by an iridium complex
Enol and vinyl esters were successfully synthesized by the use of an iridium complex as a catalyst. The reaction of carboxylic acid with terminal alkynes in the presence of catalytic amounts of [Ir(cod)Cl]2 and Na2CO3 gave the corresponding 1-alkenyl esters. The addition of carboxylic acids to alkynes principally took place in the Markovnikov fashion. In addition, by the use of an Ir complex combined with NaOAc various vinyl esters were prepared through the transvinylation between carboxylic acids and vinyl acetate.
Nakagawa, Hideto,Okimoto, Yoshio,Sakaguchi, Satoshi,Ishii, Yasutaka
p. 103 - 106
(2007/10/03)

Rate constants for the β-elimination of tosyl radical from a variety of substituted carbon-centered radicals
The rate constants for the β-elimination of tosyl radical (Ts?) from a series of carbon-centered radicals have been determined by using the radical clock methodology. Depending on the substituents R in Ts-CH2-CH(?)R radicals, the rate constants at 293 K vary by more than 2 orders of magnitude in the range of 103-106 s-1. The lowest values were found for the 2-naphthyl and carbamoyl substituents, whereas the benzyl substituent is located at the other extremity. The effect of the substituent upon the stabilization of the starting radical exerts a predominant influence in this reaction in decreasing the rate of fragmentation.
Timokhin, Vitaliy I.,Gastaldi, Stephane,Bertrand, Michele P.,Chatgilialoglu, Chryssostomos
p. 3532 - 3537
(2007/10/03)

The nitrosation of imidazolines and oxazolines
Nitrosation (HOAc / NaNO2) of 1-methyl-2-phenyl-2-imidazoline 8 results in cleavage of only the C-N single bond and production of N- (2-methylnitrosaminoethyl)-N-nitrosobenzamide 10. In contrast, 2- phenyl-2-oxazoline 9 nitrosates very rapidly to give products (13-16) derived from a diazonium ion arising from the exclusive cleavage of the C=N.
Loeppky, Richard N.,Cui, Wenge
p. 1845 - 1848
(2007/10/03)

Thermal Decomposition of Pentacarbonyl(1-acyloxyalkylidene)chromium(0) Complexes: Formation of Z-Enol Esters
Pentacarbonyl(1-acyloxyalkylidene)chromium(0) complexes, formed in situ by reaction of the corresponding tetramethylammonium pentacarbonyl(1-oxoalkyl)chromate(1-) salts with carboxylic acid halides, affords enol esters in moderate to good yields. In all cases examined, the Z-enol ester was obtained as the major or exclusive isomer. Addition of 1 equiv of pyridine to the reaction mixture substantially improved the Z/E ratio and, in most cases, increased the chemical yield.
S?derberg, Bj?rn C.,Liu, Jian,Ball, Thomas W.,Turbeville, Michael J.
p. 5945 - 5952
(2007/10/03)

Synthesis of higher vinyl esters from ethylene and higher carboxylic acids
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.
-
(2008/06/13)

A new methodology for the preparation of vinyl esters
A new methodology has been developed for the preparation of unsubstituted enol esters. Its application is demonstrated by the obtainment of vinyl aromatic α-amino esters. A brief investigation of the preparation of other hydrophobic vinyl esters proved successful. Because of the mild reaction conditions employed, it is believed this route should provide access to other enol esters.
Weinhouse,Janda
p. 81 - 83
(2007/10/02)

REACTION OF 10-VINYLPHENOTHIAZINE WITH BENZOYL PEROXIDE
-
Kurov, G. N.,Svyatkina, L. I.,Gaintseva, L. L.,Naumova, I. P.
p. 2542 - 2546
(2007/10/02)

2-Substituted 5-vinylpyrimidines, polymers obtainable therefrom and preparation thereof
The invention relates to 2-substituted 5-vinylpyrimidines of the formula STR1 wherein X is 2-pyridyl or 2-pyrimidyl, unsubstituted or substituted by methyl or ethyl groups. The compounds of formula (I) are suitable for the preparation of complex-forming or complexed, uncrosslinked or crosslinked polymers. Complexed polymers obtainable therefrom may be used as catalysts. Polymers complexed with Pd are particularly suitable for transvinylation reactions. Non-complexed polymers obtainable from compounds of formula (I) are suitable for use as metal ion extractors for different applications.
-
(2008/06/13)

Vinyl-substituted 2,2'-bipyridine compounds
Vinyl-substituted 2,2'-bipyridine compounds of the formula STR1 and complexes thereof with metals or metal compounds other than alkali metals or alkaline earth metals, or alkali metal compounds, or alkaline earth metal compounds are described, R1 and R2 being as defined in patent claim 1 and the vinyl group being bonded in the 4-position or 6-position. The 2,2'-bipyridine compounds (I) are suitable for the preparation of complex-forming or complexed, crosslinked or uncrosslinked polymers. Complexed polymers, obtainable from these, are used, for example, as catalysts, in particular for transvinylation reactions. Uncomplexed polymers, which can be prepared from compounds (I), are suitable as metal ion scavengers in various applications.
-
(2008/06/13)

Method for the preparation of alkenyl esters of carboxylic acids
A novel and effective catalyst system is provided for application in the preparation of alkenyl esters of carboxylic acids by transesterification reaction. The catalyst system consists of a palladium compound as the main ingredient and a cocatalyst formed of an alkali metal compound and a copper compound, at least one of which is a halide. The catalyst ingredients are adsorbed on a solid catalyst carrier, so that repeated use of the combined catalyst or a continuous operation of the reaction can easily be facilitated.
-
(2008/06/13)