769-78-8Relevant articles and documents
Novel synthesis routes for the preparation of low toxic vinyl ester and vinyl carbonate monomers
Hofecker, Andreas,Knaack, Patrick,Liska, Robert,Markovic, Marica,Ovsianikov, Aleksandr,Steinbauer, Patrick
supporting information, p. 3629 - 3641 (2020/10/02)
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.
Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II): Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption
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)
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.
Normal Alpha Olefin Synthesis Using Dehydroformylation or Dehydroxymethylation
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Paragraph 0127; 0128; 0129, (2019/09/06)
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.
Oxidative Dehydroxymethylation of Alcohols to Produce Olefins
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Paragraph 0057; 0058, (2019/09/06)
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.
Eco-environmental synthesis of vinyl benzoate through transesterification catalyzed by Pd/C catalyst
Gao, Jun,Guan, Dongrui,Xu, Dongmei,Zhao, Liwen,Zhang, Lianzheng,Li, Min
, p. 351 - 359 (2018/09/06)
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.
Reusable rhodium catalyst for the selective transvinylation of sp2-C linked carboxylic acid
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)
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.
Regio- and Stereoselective Chan-Lam-Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines
Steemers, Luuk,Wijsman, Linda,van Maarseveen, Jan H.
supporting information, p. 4241 - 4245 (2018/10/02)
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.).
Tandem Catalysis: Transforming Alcohols to Alkenes by Oxidative Dehydroxymethylation
Wu, Xuesong,Cruz, Faben A.,Lu, Alexander,Dong, Vy M.
supporting information, p. 10126 - 10130 (2018/08/23)
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.
Method for synthesizing vinyl carboxylate
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Paragraph 0045; 0046, (2018/04/26)
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.
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
Rej, Supriya,Pramanik, Suman,Tsurugi, Hayato,Mashima, Kazushi
supporting information, p. 13157 - 13160 (2017/12/26)
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.
