820-71-3Relevant academic research and scientific papers
METHOD FOR PRODUCING 1-ACYLOXY-2-METHYL-2-PROPENE
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Paragraph 0101-0104; 0107-0112, (2021/09/26)
A method for producing a 1-acyloxy-2-methyl-2-propene represented by the following general formula (II), including reacting a carboxylic acid represented by the following general formula (I), isobutylene, and oxygen, in the presence of a catalyst, in a liquid phase, with an amount of the isobutylene used of more than 1 mol and 50 mol or less per 1 mol of the carboxylic acid.
Method for preparing 2-methyl-1, 3-propylene glycol from isobutene
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Paragraph 0054-0056; 0058; 0064-0065; 0067-0068; 0070-0071;, (2021/02/10)
The invention discloses a method for preparing 2-methyl-1, 3-propylene glycol from isobutene. The method comprises the following steps: mixing isobutene with acetic acid and oxygen, and carrying out an oxyacetylation reaction under the action of a supported palladium-molybdenum catalyst to obtain 2-methylene propane-1, 3-diacetoxy, namely a compound (C); carrying out transesterification on the compound (C) under the action of a basic catalyst to obtain 2-methylene-1, 3-propylene glycol, namely a compound (D); and carrying out hydrogenation reaction on the compound (D) to obtain the 2-methyl-1,3-propylene glycol. According to the method, the 2-methyl-1, 3-propylene glycol can be generated with high selectivity, and the whole process is high in atom utilization rate, environmentally friendly and suitable for large-scale industrial application.
Method for preparing methallyl alcohol by using in-situ generated Cu (I) catalyst
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Paragraph 0026-0029, (2020/06/16)
The invention relates to a method for preparing methallyl alcohol by using an in-situ generated Cu (I) catalyst, which comprises the following steps: (1) dissolving a bivalent copper salt in water, adding a reducing organic matter, stirring, and dropwisely adding an obtained mixture into a methallyl alcohol preparation system; or (2) in themethallyl alcohol preparation system, adding thebivalent copper salt, then dropwise adding a reduced organic matter aqueous solution, and carrying out a catalytic reaction; or (3) in themethylallyl alcohol preparation system, adding a reduced organic matteraqueous solution, then dropwise adding a bivalent copper salt aqueous solution, and carrying out a catalytic reaction; or (4) mixing asolid bivalent copper salt with asolid reduced organic matter in proportion, adding an obtained mixture into themethallyl alcohol preparation system in batches, and carrying out catalytic reaction. The reaction system has the characteristics of high activity and high selectivity, can significantly improvethe conversion rate and selectivity of methylallyl alcohol, reducethe generation of by-product methylallyl ether, significantly reduces the synthesis cost by replacing monovalent copper with bivalent copper, and improve the market competitiveness.
Sequential Palladium-Catalyzed Allylic Alkylation/retro-Dieckmann Fragmentation Strategy for the Synthesis of α-Substituted Acrylonitriles
Katsina, Tania,Sharma, Sachi Prem,Buccafusca, Roberto,Quinn, Derek J.,Moody, Thomas S.,Arseniyadis, Stellios
supporting information, p. 9348 - 9352 (2019/11/20)
A straightforward synthesis of α-substituted acrylonitriles is described using 4-cyano-3-oxotetrahydro-thiophene (c-THT) as an acrylonitrile surrogate. This unprecedented two-step sequence featuring a palladium-catalyzed allylic alkylation (Pd-AA) and a retro-Dieckmann fragmentation provides a general entry into diversely substituted 1,4-dienes.
Palladium-Catalyzed Asymmetric Allylic Alkylation of 4-Substituted Isoxazolidin-5-ones: Straightforward Access to β2,2-Amino Acids
Nascimento de Oliveira, Marllon,Arseniyadis, Stellios,Cossy, Janine
supporting information, p. 4810 - 4814 (2018/03/21)
We report here an unprecedented and highly enantioselective palladium-catalyzed allylic alkylation applied to 4-substituted isoxazolidin-5-ones. Ultimately, the process provides a straightforward access to β2,2-amino acids bearing an all-carbon quaternary stereogenic center in great yields and a high degree of enantioselectivity.
Highly Enantioselective, Base-Free Synthesis of α-Quaternary Succinimides through Catalytic Asymmetric Allylic Alkylation
Song, Tao,Arseniyadis, Stellios,Cossy, Janine
supporting information, p. 8076 - 8080 (2018/06/15)
The synthesis of diversely substituted five-membered ring succinimide derivatives is reported featuring a direct, base-free, palladium-catalyzed asymmetric allylic alkylation. The method allows a straightforward access to the desired heterocyclic scaffold bearing an all-carbon α-quaternary stereogenic center in high yields and good to excellent enantioselectivities. To further demonstrate the synthetic utility of the method, the allylated products were further converted to various versatile chiral building blocks, including a chiral pyrrolidine and a spirocyclic derivative, using selective transformations.
Scalable Microwave-Assisted Johnson-Claisen Rearrangement with a Continuous Flow Microwave System
Egami, Hiromichi,Tamaoki, Souma,Abe, Masato,Ohneda, Noriyuki,Yoshimura, Takeo,Okamoto, Tadashi,Odajima, Hiromichi,Mase, Nobuyuki,Takeda, Kazuhiro,Hamashima, Yoshitaka
supporting information, p. 1029 - 1033 (2018/08/03)
We demonstrated the rapid Johnson-Claisen rearrangement of allyl alcohol and triethyl orthoacetate with a continuous flow apparatus combined with a microwave reactor. The reaction could be carried out without solvent, and only a catalytic amount of acetic acid was sufficient to promote the reaction under microwave irradiation conditions. To confirm the optimal reaction conditions found experimentally, we performed Design of Experiments (DoE) by the Nelder-Mead method and a least-squares method regarding the amount of acetic acid and the flow rate. Consequently, the highest yield of the desired γ,δ-unsaturated ester was obtained, and the productivity at the reaction step of the continuous process was 89.5 g/h under the optimal conditions, suggesting that 2.1 kg of the product would be theoretically obtained in 1 day. We also investigated the Johnson-Claisen rearrangement using other allylic alcohols, and the corresponding products were obtained in good to high yields per unit of time.
Method for preparing methallyl alcohol and amide simultaneously
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Paragraph 0022-0023, (2017/11/29)
A method for preparing methallyl alcohol and amide simultaneously is characterized in that methylallyl carboxylate taken as a raw material and an amine compound taken as an ammonolysis agent react under the action of a catalyst to produce methallyl alcohol and an amide compound. The methylallyl carboxylate and the amine compound taken as the ammonolysis agent are firstly adopted, and the methallyl alcohol and the amide compound are obtained under the action of the catalyst. The reaction process is a bulk reaction, no solvents are added, almost no wastewater or salt are produced, and byproduct methyl allyl ether is not produced; the defect that a large number of wastewater is produced through hydrolysis is overcome due to adoption of ammonolysis, the methallyl alcohol and the amide compound are coproduced directly by use of ammonoysis, coupling production is realized, and the cost is reduced.
Radical Cyclization of Epoxy Vinyl- and Allylsulfones Promoted by Titanocene Chloride
Fernández-Mateos,Madrazo, S. Encinas,Teijón, P. Herrero,González, R. Rubio
, p. 4378 - 4391 (2015/05/13)
A titanocene-mediated intramolecular radical addition of different epoxy vinyl- and allylsulfones has been achieved. Five- and six-membered ring products were obtained in good to excellent yields in the presence of both 2.2 and 0.2 equiv of Cp2TiCl. A novel double-activation strategy allowed us to achieve small-size rings such as cyclobutanes and cyclopropanes. (Chemical Equation Presented).
Hydroxyl-directed stereoselective diboration of alkenes
Blaisdell, Thomas P.,Caya, Thomas C.,Zhang, Liang,Sanz-Marco, Amparo,Morken, James P.
supporting information, p. 9264 - 9267 (2014/07/21)
An alkoxide-catalyzed directed diboration of alkenyl alcohols is described. This reaction occurs in a stereoselective fashion and is demonstrated with cyclic and acyclic homoallylic and bishomoallylic alcohol substrates. After oxidation, the reaction generates 1,2-diols such that the process represents a method for the stereoselective directed dihydroxylation of alkenes.
