110-67-8Relevant academic research and scientific papers
Phosphine-catalyzed hydration and hydroalkoxylation of activated olefins: Use of a strong nucleophile to generate a strong base
Stewart, Ian C.,Bergman, Robert G.,Toste, F. Dean
, p. 8696 - 8697 (2003)
The direct addition of water and a variety of alcohols to activated olefins was observed in the presence of nucleophilic phosphine catalysts. Unlike existing methods, the reactions proceed at room temperature and in the absence of transition metals, or strong acids or bases. The use of simple commercially available catalysts makes this an attractive method for the preparation of β-hydroxy and β-alkoxy substrates, which are prevalent targets and intermediates in organic synthesis. The scope and mechanism of this reaction has been explored, and the compound that acts as the resting state of the catalyst was synthesized independently. Our mechanism also suggests the possibility of extending the scope of this reactivity to other classes of nucleophiles. Copyright
Addition of alcohols to acrylic compounds catalyzed by Mg-Al LDH
Teodorescu,Deaconu,Bartha,Z?voianu,Pavel
, p. 117 - 122 (2014)
This study reports the preparation of hydrotalcite with Mg/Al molar ratio 3 by co-precipitation under low suprasaturation conditions of Mg and Al nitrated solutions with Na2CO3 and NaOH at pH 10. The solid was thermally decomposed at 460°C in air atmosphere in order to obtain mixed oxides which, by means of memory effect, can reconstruct the hydrotalcite structure by hydration with bidistilled water. The hydrotalcite and reconstructed samples by memory effect were characterized by elemental analysis, powder XRD, DRIFT and TG-DTG. Determination of the catalysts surface base sites was made using a method based on the irreversible adsorption of organic acids with different pKa values and N2 adsorption-desorption isotherms. The catalytic activity of these solids was evaluated in 1,4-addition of saturated linear alcohols to different acrylic compounds. All these reactions arose with high selectivity in the desired product. No by-products were detected by means of GC-MS chromatography and 1H NMR.
Preparation method of 3-methoxypropylamine
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Paragraph 0047-0049; 0055-0056; 0058-0059; 0061-0062; ..., (2021/06/23)
The invention discloses a preparation method of 3-methoxylpropylamine. The method comprises the following steps: carrying out addition on methanol and acrylonitrile to prepare a 3-methoxylpropionitrile crude product, and then carrying out catalytic hydrogenation on the crude product by using a Raney catalyst to prepare the 3-methoxylpropylamine. In the addition reaction, through air protection and gradient temperature reaction control, the acrylonitrile conversion rate of the addition reaction can be increased, generation of hydrogenation reaction by-products is reduced, the acrylonitrile conversion rate is larger than 99.6%, the yeild of the 3-methoxylpropylamine is larger than 99.1% and residual quantity of acrylonitrile in the crude product is smaller than 0.3%; and the hydrogenation reaction raw materials do not need to be refined, an alkaline auxiliary agent does not need to be additionally added, the average yield of MOPA can reach 96.5%, and the catalyst can be recycled for more than 30 batches.
KOtBu-Catalyzed Michael Addition Reactions Under Mild and Solvent-Free Conditions
Thiyagarajan, Subramanian,Krishnakumar, Varadhan,Gunanathan, Chidambaram
supporting information, p. 518 - 523 (2020/02/04)
Designed transition metal complexes predominantly catalyze Michael addition reactions. Inorganic and organic base-catalyzed Michael addition reactions have been reported. However, known base-catalyzed reactions suffer from the requirement of solvents, additives, high pressure and also side-reactions. Herein, we demonstrate a mild and environmentally friendly strategy of readily available KOtBu-catalyzed Michael addition reactions. This simple inorganic base efficiently catalyzes the Michael addition of underexplored acrylonitriles, esters and amides with (oxa-, aza-, and thia-) heteroatom nucleophiles. This catalytic process proceeds under solvent-free conditions and at room temperature. Notably, this protocol offers an easy operational procedure, broad substrate scope with excellent selectivity, reaction scalability and excellent TON (>9900). Preliminary mechanistic studies revealed that the reaction follows an ionic mechanism. Formal synthesis of promazine is demonstrated using this catalytic protocol.
Preparation method of gamma-methoxypropylamine
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Paragraph 0025; 0027-0028; 0036-0037; 0045-0046; 0054-0055, (2019/03/28)
The invention provides a preparation method of gamma-methoxypropylamine, which is high in conversion rate. The invention adopts the following technical scheme: the preparation method of the gamma-methoxypropylamine, comprising the following steps: preparing 3-methoxypropionitrile by using acrylonitrile and sodium methoxide as raw materials; and by taking the 3-methoxypropionitrile as a raw material, preparing the gamma-methoxypropylamine in the presence of an amine reagent, a nickel catalyst and silver nitrate in a reducing manner. The raw materials are high in utilization rate; the separationprocess is simple and clear; the energy consumption is low; the production cost of a product is low; and the solvent and the catalyst can be recycled for use.
Formation of a New, Strongly Basic Nitrogen Anion by Metal Oxide Modification
Tamura, Masazumi,Kishi, Ryota,Nakayama, Akira,Nakagawa, Yoshinao,Hasegawa, Jun-Ya,Tomishige, Keiichi
supporting information, p. 11857 - 11867 (2017/09/08)
Development of new hybrid materials having unique and unprecedented catalytic properties is a challenge for chemists, and heterogeneous-homogeneous hybrid catalysts have attracted much attention because of the preferable and exceptional properties that are highly expected to result from combination of the components. Base catalysts are widely used in organic synthesis as key materials, and a new class of base catalysts has made a large impact from academic and industrial viewpoints. Here, a principle for creating a new strong base by hybridization of homogeneous and heterogeneous components is presented. It is based on the modification of organic compounds with metal oxides by using the acid-base property of metal oxides. Based on kinetic and DFT studies, combination of CeO2 and 2-cyanopyridine drastically enhanced the basicity of 2-cyanopyridine by a factor of about 109 (～9 by pKa (in CH3CN)), and the pKa was estimated to be ～21, which locates it in the superbase category. 2-Cyanopyridine and CeO2 formed a unique adsorption complex via two interaction modes: (i) coordinative interaction between the Ce atom of CeO2 and the N atom of the pyridine ring in 2-cyanopyridine, and (ii) covalent interaction between the surface O atom of CeO2 and the C atom of the CN group in 2-cyanopyridine by addition of the lattice oxygen of CeO2 to the CN group of 2-cyanopyridine. These interactions established a new, strongly basic site of N- over the CeO2 surface.
Synthesis method of 3-methoxyl-N, N-dimethylacrylamide
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Paragraph 0039; 0042-0044, (2017/07/22)
The invention relates to a synthesis method of 3-methoxyl-N, N-dimethylacrylamide, and belongs to the technical field of chemical synthesis. The synthesis method comprises the following steps of adding 3-methoxypropionic acid and dimethylamine into a sealed reactor; raising the temperature to 80 to 150 DEG C; performing reaction to obtain 3-methoxyl-N, N-dimethylacrylamide, wherein the pressure in the sealed reactor is 0.1 to 10.0MPa. The 3-methoxypropionic acid is used as the raw materials to perform high-temperature dewatering with dimethylamine in a sealed reaction vessel; polyhydric alcohol and basic catalysts are not needed; the reaction is simple; the implementation is easy; the yield of a product is high; the purity is high; the high yield is realized; meanwhile, the pollution is little; the cost is low; the method conforms to the requirements of modern chemical green synthesis. Meanwhile, the 3-methoxypropionic acid uses low-price acrylonitrile as the starting raw materials; the acrylonitrile is subjected to alkoxylation to obtain methoxyl propionitrile; then, hydrolysis is performed. The operation is simple; the energy consumption is low.
3-methoxy-N,N-dimethylacrylamide synthesis method
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Paragraph 0037; 0041; 0042, (2017/08/29)
The invention belongs to the technical field of chemical synthesis and relates to a 3-methoxy-N,N-dimethylacrylamide synthesis method. The method includes steps: adding acrylonitrile, absolute methanol and metal alkoxide into a reactor for reaction, recovering unreacted absolute methanol to obtain 3-methoxypropionitrile; adding acid catalysts and water into 3-methoxypropionitrile, heating for hydrolysis reaction, and filtering to obtain 3-methoxypropionic acid; adding 3-methoxypropionic acid and dimethylamine into a closed reactor, heating for reaction to obtain 3-methoxy-N,N-dimethylacrylamide. By adoption of cheap acrylonitrile as a starting material, the acrylonitrile is subjected to alkoxylation to obtain methoxypropionitrile which is then hydrolyzed to obtain methoxypropionic acid, and acid-base reaction, salification and dehydration are performed to obtain a target product without consumption of polyhydric alcohols and alkaline catalysts. High-temperature dehydration can be realized in the closed reactor, simplicity and feasibility in reaction are achieved, and high product yield and high purity are realized.
Efficient and rapid synthesis of phenolic analogs of 4-phenylbutanoic acid using microwave-assisted Michael addition as a key reaction
Iida, Hirokazu,Akatsu, Yusuke,Mizukami, Kazushi,Natori, Sho,Matsukawa, Minako,Takahashi, Kie
, p. 581 - 585 (2016/07/06)
ABSTRACT: The addition of phenols to acrylonitrile in the presence of aqueous benzyltrimethylammonium hydroxide or tetramethylammonium hydroxide under microwave irradiation yielded the corresponding Michael adducts. The obtained adducts were easily transformed to phenolic analogs of 4-phenylbutanoic acids via the hydrolysis of nitrile groups.
Catalytic Olefin hydroalkoxylation by nano particles of pollucite
Zamanian, Sara,Kharat, Ali Nemati
, p. 981 - 986 (2015/06/25)
The catalytic hydroalkoxylation of α,β-unsaturated esters, nitriles, and ethers with aliphatic and aromatic alcohols over pollucite using thermal and microwave-assisted methods was investigated. To study the effect of the alcohol structures on the mechanism of the hydroalkoxylation reaction, different alcohols, such as methanol to butanol, cyclohexanol, phenol, and 2-ethylhexanol were used. The activities of pollucite, in contrast to other basic solids, were scarcely affected by the presence of air and moisture. The correlation between alcohol acidity and reaction activity is discussed. The prepared pollucite was characterized by X-ray diffraction, volumetric nitrogen adsorption surface area analysis, and CO2 temperature-programmed desorption. Scanning electron microscopy analysis revealed that the size of the modified nano catalyst particles was under 40nm.
