1120-97-4Relevant articles and documents
Application of empirical and quantum-chemical computational methods in the determination of the free conformational energy of substituents in 1,3-dioxanes
Kuznetsov,Alekseeva
, p. 713 - 720 (2003)
The advantages and disadvantages of empirical and quantum-chemical methods for the determination of the free conformational energy of methyl and phenyl substituents at the C(4) and C(5) atoms of the ring in the molecules of 1,3-dioxanes are analyzed.
Synthesis and bactericidal activity of substituted cyclic acetals
Tugarova,Kazakova,Kamnev,Zlotskii
, p. 1930 - 1933 (2014)
A series of substituted cyclic acetals were synthesized and tested for their bactericidal activity against bacteria strain Azospirillum brasilense Sp245.
Biomass alcoholysis method for petroleum-based plastic POM
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Paragraph 0030-0051, (2021/05/01)
The invention discloses a biomass alcoholysis method for petroleum-based plastic POM. According to the method, simple biomass derivative alcohol and the petroleum-based plastic POM are allowed to generate a cyclic acetal product through dehydration condensation under catalytic conditions; low reaction cost and high added value are realized, and only water is byproduced and is easy to separate; and an obtained product has high added value, can be used for preparing organic solvents such as lignin and chromatographic analysis solvents, metal surface treatment agents or medical intermediates and monomers, realizes green, efficient and low-cost recovery, and has a high practical application value.
Method for synthesizing 1, 3-dihydric alcohol by using olefin and methanol as raw materials
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Paragraph 0094-0120, (2021/07/28)
The invention discloses a method for preparing 1, 3-dihydric alcohol by taking olefin and methanol as raw materials through one-step reaction and a catalyst for the method. The method comprises the following steps: 1) adding a catalyst into a reactor, heating and reducing in a hydrogen-nitrogen mixed atmosphere, then cooling to 60-180 DEG C, and keeping the pressure in the reactor to be 0.5-8 MPa for reaction; 2) respectively introducing olefin and a methanol aqueous solution into the reactor for reaction, wherein the airspeed is 0.01-10h in terms of methanol; 3) enabling that the reaction product enters a product storage tank after condensation and gas-liquid separation; and 4) carrying out rectification separation on the reaction product obtained in the step 3) to obtain a 1, 3-dihydric alcohol product with the purity of more than 99%. The method provided by the invention has the advantages of low raw material cost, simple steps and continuous production.
Efficient Plastic Waste Recycling to Value-Added Products by Integrated Biomass Processing
Beydoun, Kassem,Klankermayer, Jürgen
, p. 488 - 492 (2020/01/24)
The industrial production of polymeric materials is continuously increasing, but sustainable concepts directing towards a circular economy remain rather elusive. The present investigation focuses on the recycling of polyoxymethylene polymers, facilitated through combined catalytic processing of polymer waste and biomass-derived diols. The integrated concept enables the production of value-added cyclic acetals, which can flexibly function as solvents, fuel additives, pharmaceutical intermediates, and even monomeric materials for polymerization reactions. Based on this approach, an open-loop recycling of these waste materials can be envisaged in which the carbon content of the polymer waste is efficiently utilized as a C1 building block, paving the way to unprecedented possibilities within a circular economy of polyoxymethylene polymers.
Ruthenium-Catalyzed Synthesis of Cyclic and Linear Acetals by the Combined Utilization of CO2, H2, and Biomass Derived Diols
Beydoun, Kassem,Klankermayer, Jürgen
supporting information, p. 11412 - 11415 (2019/07/18)
Herein a transition-metal catalyst system for the selective synthesis of cyclic and linear acetals from the combined utilization of carbon dioxide, molecular hydrogen, and biomass derived diols is presented. Detailed investigations on the substrate scope enabled the selectivity of the reaction to be largely guided and demonstrated the possibility of integrating a broad variety of substrate molecules. This approach allowed a change between the favored formation of cyclic acetals and linear acetals, originating from the bridging of two diols with a carbon-dioxide based methylene unit. This new synthesis option paves the way to novel fuels, solvents, or polymer building blocks, by the recently established “bio-hybrid” approach of integrating renewable energy, carbon dioxide, and biomass in a direct catalytic transformation.
Zeolite-Catalyzed Formaldehyde–Propylene Prins Condensation
Vasiliadou, Efterpi S.,Gould, Nicholas S.,Lobo, Raul F.
, p. 4417 - 4425 (2017/11/20)
Prins condensation of formaldehyde with propylene to form 3-buten-1-ol is investigated using microporous solid acid catalysts. Zn/H-beta shows high conversion but leads to a broad product distribution composed primarily of pyrans. Mechanistic studies revealed that 3-buten-1-ol reacts via Prins cyclization or dehydrate to 1,3-butadiene that further reacts with formaldehyde via a hetero-Diels–Alder reaction. These secondary reactions are suppressed over ZSM-5 catalysts: 3-buten-1-ol is the predominant product over H-ZSM-5 zeolite under all conditions investigated. 3-Buten-1-ol selectivity of up to 75 % is achieved. In a second step 3-buten-1-ol dehydrates at temperatures as low as 423 K, forming 1,3-butadiene. Although Br?nsted acid sites are the primary catalytic sites, ion exchange of ZnII increases the overall rate and 3-buten-1-ol selectivity. H-ZSM-5 showed significant differences in reactivity and selectivity as a function of the Si/Al ratio; optimal catalytic properties were observed within Si/Al=40–140.
Heterogeneous ceria catalyst with water-tolerant Lewis acidic sites for one-pot synthesis of 1,3-diols via prins condensation and hydrolysis reactions
Wang, Yehong,Wang, Feng,Song, Qi,Xin, Qin,Xu, Shutao,Xu, Jie
, p. 1506 - 1515 (2013/03/28)
The use of a heterogeneous Lewis acid catalyst, which is insoluble and easily separable during the reaction, is a promising option for hydrolysis reactions from both environmental and practical viewpoints. In this study, ceria showed excellent catalytic activity in the hydrolysis of 4-methyl-1,3-dioxane to 1,3-butanediol in 95% yield and in the one-pot synthesis of 1,3-butanediol from propylene and formaldehyde via Prins condensation and hydrolysis reactions in an overall yield of 60%. In-depth investigations revealed that ceria is a water-tolerant Lewis acid catalyst, which has seldom been reported previously. The ceria catalysts showed rather unusual high activity in hydrolysis, with a turnover number (TON) of 260, which is rather high for bulk oxide catalysts, whose TONs are usually less than 100. Our conclusion that ceria functions as a Lewis acid catalyst in hydrolysis reactions is firmly supported by thorough characterizations with IR and Raman spectroscopy, acidity measurements with IR and 31P magic-angle-spinning NMR spectroscopy, Na+/H + exchange tests, analyses using the in situ active-site capping method, and isotope-labeling studies. A relationship between surface vacancy sites and catalytic activity has been established. CeO2(111) has been confirmed to be the catalytically active crystalline facet for hydrolysis. Water has been found to be associatively adsorbed on oxygen vacancy sites with medium strength, which does not lead to water dissociation to form stable hydroxides. This explains why the ceria catalyst is water-tolerant.
Reactions of cyclic boric acids esters with paraformaldehyde
Brusilovskii, Yu. E.,Kuznetsov
experimental part, p. 542 - 544 (2011/06/22)
Reactions of five- and six-membered cyclic esters of boric acids with paraformaldehyde lead to the corresponding 1,3-dioxacycloalkanes. It is shown that trans-isomers of 2,4,5-substituted 1,3,2-dioxaborinanes react faster than their cis-isomers.
Acetolysis of Cyclic Acetals: Regioselective Acylative Cleavage of Cyclic Formals
Bailey, William F.,Rivera, Alberto D.
, p. 4958 - 4964 (2007/10/02)
The acid-catalyzed reaction of cyclic acetals with acetic anhydride has been investigated.Acylative cleavage of cyclic formals has been found to be a clean, high-yield reaction involving rupture of the C(2)-O bond with loss of stereochemical integrity at the C(2)-position to give hemiacetal acetate products.Ring cleavage of unsymmetrically substituted cyclic formals with either acetic anhydride or acetyl chloride occurs via preferential rupture of the less congested C(2)-O bond (Scheme I, path A).Such cleavage is totally regiospecific for 1,3-dioxanes and displays high (75-85percent) regioselectivity for smaller and larger ring systems.Acetolysis of cyclic acetals other than formals is a slow process that leads to loss of the aldehyde derived fragment and formation of simple diacetates.These results are rationalized in terms of rate-limiting electrophilic attack that is acutely sensitive to steric effects engendered by substituents located at positions adjacent to ring oxygens.
