2051-76-5Relevant articles and documents
Polymerization of free secondary amine bearing monomers by RAFT polymerization and other controlled radical techniques
Janoschka, Tobias,Teichler, Anke,Krieg, Andreas,Hager, Martin D.,Schubert, Ulrich S.
, p. 1394 - 1407 (2012)
This work describes the polymerization of the free secondary amine bearing monomer 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPMA) by means of different controlled radical polymerization techniques (ATRP, RAFT, NMP). In particular, reversible addition-fragmentation chain transfer (RAFT) polymerization enabled a good control at high conversions and a polydispersity index below 1.3, thereby enabling the preparation of well-defined polymers. Remarkably, the polymerization of the secondary amine bearing methacrylate monomer was not hindered by the presence of the free amine that commonly induces degradation of the RAFT reagent. Subsequent oxidation of the polymer yielded the polyradical poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate), which represents a valuable material used in catalysis as well as for modern batteries. The obtained polymers having a molar mass (Mn) of 10,000-20,000 g/mol were used to fabricate well-defined, radical-bearing polymer films by inkjet- printing.
Design and regioselective synthesis of (2-Bromo-2-alkoxycarbonyl)ethyl acrylates as inimers for hyperbranched (Co)polyacrylates
Pugh, Coleen,Raveendra, Bindu,Singh, Anirudha,Samuel, Reichel,Garcia, Guillermina
, p. 1947 - 1950 (2010)
A route based on deaminohalogenation of serine is established to synthesize bromoinimers that can be homopolymerized to produce hyperbranched polyacrylates that are true architectural analogues of linear polyacrylates; that is, an ester group is attached to every other carbon along the polymer backbone, and each repeat unit contains a free ester side chain. Georg Thieme Verlag Stuttgart.
Suppression of chain transfer in catalytic acrylate polymerization via rapid and selective secondary insertion
Jian, Zhongbao,Baier, Moritz C.,Mecking, Stefan
, p. 2836 - 2839 (2015)
In catalytic copolymerization, undesired chain transfer after incorporation of a polar vinyl monomer is a fundamental problem. We show an approach to overcome this problem by a fast consecutive insertion. The second double bond of acrylic anhydride rapidly inserts intramolecularly to regio- and stereoselectively form a cyclic repeat unit and a primary alkyl favorable for chain growth (>96%). This results in significantly enhanced copolymer molecular weights vs monofunctional acrylate monomers.
An efficient synthesis of chiral isoquinuclidines by Diels - Alder reaction using Lewis acid catalyst
Hirama, Masafumi,Kato, Yuji,Seki, Chigusa,Nakano, Hiroto,Takeshita, Mitsuhiro,Oshikiri, Noriko,Iyoda, Masahiko,Matsuyama, Haruo
, p. 7618 - 7624 (2010)
The Diels-Alder reaction of 1,2-dihydropyridine derivatives (1-phenoxycarbonyl-1,2-dihydropyridine 1 or 1-methoxycarbonyl-1,2- dihydropyridine 4) with N-acryloyl (1S)-2,10-camphorsultam (1S)-2 {or N-acryloyl (1R)-2,10-camphorsultam (1R)-2} in the presence of Lewis acid, such as titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride afforded the endo-cycloaddition product, 2-azabicyclo[2.2.2]octane derivatives in good yields with excellent diastereoselectivity. The absolute stereochemistry assignment of the endo-cycloaddition product (1S)-5a starting from N-acryloyl (1S)-2,10-camphorsultam (1S)-2 has been established to be (1S,4R,7S) and the reaction mechanism was proposed.
Synthesis and structural characterization of a monocarboxylic inhibitor for GRB2 SH2 domain
Haura, Eric B.,Ji, Haitao,Li, Zilu,Schonbrunn, Ernst,Sun, Luxin,Xiao, Tao,Zhang, Min
supporting information, (2021/09/14)
A monocarboxylic inhibitor was designed and synthesized to disrupt the protein–protein interaction (PPI) between GRB2 and phosphotyrosine-containing proteins. Biochemical characterizations show compound 7 binds with the Src homology 2 (SH2) domain of GRB2 and is more potent than EGFR1068 phosphopeptide 14-mer. X-ray crystallographic studies demonstrate compound 7 occupies the GRB2 binding site for phosphotyrosine-containing sequences and reveal key structural features for GRB2–inhibitor binding. This compound with a –1 formal charge offers a new direction for structural optimization to generate cell-permeable inhibitors for this key protein target of the aberrant Ras-MAPK signaling cascade.
Automated Assembly of Starch and Glycogen Polysaccharides
Delbianco, Martina,Seeberger, Peter H.,Zhu, Yuntao
supporting information, p. 9758 - 9768 (2021/06/30)
Polysaccharides are Nature's most abundant biomaterials essential for plant cell wall construction and energy storage. Seemingly minor structural differences result in entirely different functions: cellulose, a β (1-4) linked glucose polymer, forms fibrils that can support large trees, while amylose, an α (1-4) linked glucose polymer forms soft hollow fibers used for energy storage. A detailed understanding of polysaccharide structures requires pure materials that cannot be isolated from natural sources. Automated Glycan Assembly provides quick access to trans-linked glycans analogues of cellulose, but the stereoselective installation of multiple cis-glycosidic linkages present in amylose has not been possible to date. Here, we identify thioglycoside building blocks with different protecting group patterns that, in concert with temperature and solvent control, achieve excellent stereoselectivity during the synthesis of linear and branched α-glucan polymers with up to 20 cis-glycosidic linkages. The molecules prepared with the new method will serve as probes to understand the biosynthesis and the structure of α-glucans.
Multicatalytic Transformation of (Meth)acrylic Acids: a One-Pot Approach to Biobased Poly(meth)acrylates
Fouilloux, Hugo,Placet, Vincent,Qiang, Wei,Robert, Carine,Thomas, Christophe M.
supporting information, p. 19374 - 19382 (2021/07/21)
Shifting from petrochemical feedstocks to renewable resources can address some of the environmental issues associated with petrochemical extraction and make plastics production sustainable. Therefore, there is a growing interest in selective methods for transforming abundant renewable feedstocks into monomers suitable for polymer production. Reported herein are one-pot catalytic systems, that are active, productive, and selective under mild conditions for the synthesis of copolymers from renewable materials. Each system allows for anhydride formation, alcohol acylation and/or acid esterification, as well as polymerization of the formed (meth)acrylates, providing direct access to a new library of unique poly(meth)acrylates.
METHOD FOR PRODUCING (METH)ACRYLIC ACID ANHYDRIDE
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Paragraph 0024-0031; 0040, (2021/05/28)
PROBLEM TO BE SOLVED: To provide an industrially useful method for producing a (meth)acrylic acid anhydride capable of producing a (meth)acrylic acid anhydride with high yield and high purity. SOLUTION: There is provided a method for producing a (meth)acrylic acid anhydride by reacting a (meth)acrylic acid alkali metal salt and sulfonyl chloride in an organic solvent. The (meth)acrylic acid alkali metal salt includes lithium (meth)acrylate, sodium (meth)acrylate, potassium (meth)acrylate or the like. Among these (meth)acrylic acid alkali metal salts, preferable are sodium acrylate, potassium acrylate, sodium methacrylate and potassium methacrylate in consideration of market feedability, reactivity and easiness of treatment after the reaction. In addition, the sulfonyl chloride includes benzenesulfonyl chloride, p-toluenesulfonyl chloride and methanesulfonyl chloride. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
METHOD FOR PRODUCING N-BENZYL-2-BROMO-3-METHOXYPROPIONAMIDE AND INTERMEDIATES THEREOF
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Paragraph 0107-0109; 0136, (2020/05/02)
The present invention provides an industrially-preferable method for safely producing N-benzyl-2-bromo-3-methoxypropionamide at a high yield but at low cost. The method for producing of the present invention includes: in sequence, an amidation process that causes diacrylic anhydride to react with benzylamine in a solvent to obtain N-benzylacrylamide; a bromination process that causes N-benzylacrylamide to react with bromine in a solvent to obtain N-benzyl-2,3-dibromopropionamide; and a methoxylation process that causes N-benzyl-2,3-dibromopropionamide to react with methanol in the presence of a base to obtain N-benzyl-2-bromo-3-methoxypropionamide.
METHOD FOR PRODUCING CARBOXYLIC ACID ANHYDRIDE AND METHOD FOR PRODUCING CARBOXYLIC ACID ESTER
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Paragraph 0075; 0076, (2017/04/18)
Provided is a production method whereby corresponding carboxylic acid anhydrides and carboxylic acid esters can be obtained at high yield from various carboxylic acids even without a solvent and near room temperature. A method for producing a carboxylic acid anhydride represented by formula (II), the method comprising reacting a compound represented by formula (I) and a carboxylic acid in the presence of a Group II metal compound having an ionic ligand containing an oxygen atom. A method for producing a carboxylic acid ester, the method comprising reacting a carboxylic acid anhydride produced by the aforementioned method and an alcohol. In formula (I), R1 represents a C1-20 hydrocarbon group. In formula (II), R2 represents a C1-20 hydrocarbon group.
