- Heterogeneous Aza-Michael Addition Reaction by the Copper-Based Metal–Organic Framework (CuBTC)
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Abstract: The copper benzene-1, 3, 5-tricarboxylate metal–organic framework (CuBTC) was found to be an effective heterogeneous catalyst for the aza-Michael addition reaction of the four types of amines to electron deficient alkenes at room temperature. The catalytic protocol showed high product yields and outstanding chemo selectivity. The cyclic amines (piperidine and pyrrolidine) and aliphatic amines (n-dibutylamine) provided aza-Michael addition with a high yield of product (?98%) within shorter reaction period (2?h) at room temperature under mild reaction conditions using CuBTC. However, it was observed that the aza-Michael reaction proceeded more slowly, giving 62% yield of product after 24?h in the case of aromatic amine (aniline) with n-butyl acrylate in the presence of CuBTC under identical reaction conditions. The catalyst could be reused four recycles without losing its initial catalytic activity and selectivity. XRD and SEM analysis further confirmed that the crystallinity of catalyst was retained during the reaction. A reaction mechanism is proposed for the aza-Michael addition reaction over heterogeneous CuBTC catalyst. Graphic Abstract: [Figure not available: see fulltext.].
- Bhattacharjee, Samiran,Shaikh, Aftab Ali,Ahn, Wha-Seung
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p. 2011 - 2018
(2020/11/18)
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- Bio-heterogeneous Cu(0)NC@PHA for n-aryl/alkylation at room temperature
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A pure cellulose was derived from waste fibre and it was chemically modified to a hydroxamic acid ligand. The poly(hydroxamic acid) was treated with an aqueous copper solution to afford the greenish stable five-membered copper complex; namely Cu(II)@PHA. Further, the Cu(II)@PHA was treated with a reducing agent hydrazine hydride to give brown colour cellulose supported copper nanocomplex (Cu(0)NC@PHA). The Cu(0)NC@PHA was characterised by ATR-FTIR, FE-SEM & EDS, TEM, ICP-OES, TGA, XRD and XPS analyses. The cellulose-based Cu(0)NC@PHA was used for the n-aryl/alkylation (Michael addition) reaction with a variety of α,β-unsaturated Michael acceptors to produce the corresponding n-aryl/alkyl products with an excellent yield at room temperature. The Cu(0)NC@PHA showed extraordinary stability and it was easily filtered out from the reaction mixture and may potentially recycled up to five times without loss of its original catalytic ability.
- Jian Fui, Choong,Lutfor Rahman, Md,Musta, Baba,Sani Sarjadi, Mohd,Sarkar, Shaheen M.,Xin Ting, Tang
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- MANUFACTURING METHOD OF N-SUBSTITUTED (METH)ACRYLAMIDE
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To provide a method for industrially manufacturing high purity β-alkoxypropionic acid amide, β-aminopropionic acid amide and N-substituted (meth)acrylamide at high yield using (meth)acrylic acid ester as a starting material.SOLUTION: By conducting an amidation reaction with amine in the presence of a metal complex as a catalyst using β-substituted propionic acid ester which is a product material of a Michael addition reaction of (meth)acrylic acid ester and alcohol or amine, β-substituted propionic acid amide is obtained. Further by conducting a thermal decomposition reaction of the β-substituted propionic acid amide in the presence of the metal complex, and eliminating the alcohol or the amine, objective compound N-substituted (meth)acrylamide is obtained.SELECTED DRAWING: None
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Paragraph 0053; 0056
(2019/05/25)
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- Tapioca cellulose based copper nanoparticles for chemoselective N-alkylation
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Biomaterials as a support for catalysts are of prime importance. Tapioca root which is an abundant biopolymer source was used to synthesize cellulose supported bio-heterogeneous poly(hydroxamic acid) copper nanoparticles (CuN@PHA) and was characterized by Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-Vis), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), transmission electron microscopy (TEM) analyses. The tapioca cellulose supported CuN@PHA (50 mol ppm) effectively catalyzed N-alkylation reaction of aliphatic amines with α,β-unsaturated compounds to give the corresponding alkylated products. High yields up to 95% were achieved for the converted products. The reusability of the cellulose supported nanoparticles was found to be excellent with no significant reduction of its catalytic activity over several cycles. The catalyst showed high catalytic activity having turnover number (TON) 18000 and turnover frequency (TOF) 2250 h-1.
- Islam, Md. Shaharul,Mandal, Bablu Hira,Biswas, Tapan Kumar,Rahman, Md. Lutfor,Rashid,Tan, Suat-Hian,Sarkar, Shaheen M.
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p. 550 - 557
(2017/01/05)
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- Waste corn-cob cellulose supported bio-heterogeneous copper nanoparticles for aza-Michael reactions
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Bio-heterogeneous poly(amidoxime) copper nanoparticles were prepared on the modified surface of waste corn-cob cellulose through a graft copolymerization process. The Cu-nanoparticles (0.05 mol% to 50 mol ppm) selectively promoted the aza-Michael reaction of aliphatic amines to give the corresponding alkylated products at room temperature in methanol. The supported nanoparticles were easy to recover and reused eight times without a significant loss of their activity.
- Sarkar, Shaheen M.,Sultana,Biswas, Tapan Kumar,Rahman, Md. Lutfor,Yusoff, Mashitah Mohd
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p. 497 - 502
(2016/01/12)
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- Poly(hydroxamic acid) functionalized copper catalyzed C-N bond formation reactions
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Highly active poly(hydroxamic acid) functionalized copper catalysts were synthesized by the surface modification of khaya cellulose through graft copolymerization and subsequent hydroximation processes. The prepared catalysts were well characterized by FTIR, FESEM, HRTEM, ICP-AES, UV-vis and XPS analyses. The supported catalysts effectively promoted C-N bond formation reactions and provided excellent yields of the corresponding products under mild reaction conditions. The catalysts were easy to recover from the reaction mixture and were reused several times without any significant loss of their catalytic activity.
- Islam, Md. Shaharul,Mandal, Bablu Hira,Biswas, Tapan Kumar,Rahman, Md. Lutfor,Rashid,Tan, Suat-Hian,Sarkar, Shaheen M.
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p. 56450 - 56457
(2016/07/06)
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- (Meth) acrylamide hydroxyakyl production (by machine translation)
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PROBLEM TO BE SOLVED: To provide a method of manufacturing hydroxyalkyl (meth) acrylamide which uses dibutyl amine as a double bond protecting reagent, and thereby can stably carry out thermal decomposition of an amide adduct without an acid catalyst. SOLUTION: In the method, methyl (meth)acrylate and dialkylamine are reacted to convert into an ester adduct, the adduct is made to react with alkanolamine under the presence of a strong base nature catalyst, an amide adduct which is a synthetic intermediate is obtained after the sulfuric acid neutralizing of the ester adduct, and then thermal decomposition of the amide adduct is carried out to manufacture hydroxyalkyl (meta) acrylamide. Dibutyl amine is used for double bond protecting of methyl (meth)acrylate, and thereby thermal decomposition of the amide adduct obtained thereafter can be carried out stably without using an acid catalyst to obtain hydroxyalkyl (meth) acrylamide. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0019
(2016/12/12)
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- Carboxylate-assisted formation of alkylcarbonate species from co 2 and tetramethylammonium salts with a β-amino acid anion
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Tetramethylammonium-based molten salts bearing a β-amino acid anion (TMAAs) are synthesized through Michael addition reactions of amines with methyl acrylate followed by hydrolysis and subsequent neutralization by using aqueous tetramethylammonium hydroxide. The CO2 capture performances of the TMAAs are evaluated and are shown to interact with CO2 in a 1:1 mode in both water and alcohol. FTIR and 13C NMR spectroscopic studies on the interactions of TMAAs with CO2 indicate that the type of CO 2 adduct varies with the solvent used. When water is used as the solvent, a bicarbonate species is produced, whereas hydroxyethylcarbonate and methylcarbonate species are generated in ethylene glycol and methanol, respectively. Computational calculations show that the carboxylate groups of TMAAs contribute towards the formation and stabilization of 1:1 CO2 adducts through hydrogen bonding interactions with the hydrogen atoms of the amino groups.
- Hong, Sung Yun,Cheon, Youngeun,Shin, Seung Hoon,Lee, Hyunjoo,Cheong, Minserk,Kim, Hoon Sik
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p. 890 - 897
(2013/07/27)
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- An efficient biomaterial supported bifunctional organocatalyst (ES-SO 3- C5H5NH+) for the synthesis of β-amino carbonyls
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A biomaterial supported organocatalyst, readily synthesized by the reaction of chemically modified sulfonic group containing expanded corn starch with pyridine exhibited excellent catalytic activity for the synthesis of β-amino carbonyls in excellent yields via aza-Michael addition of amines to electron deficient alkenes. A remarkable enhancement in the reaction rates was observed with the prepared bifunctional organocatalyst in comparison to the either starch grafted sulfonic acid or the corresponding homogeneous pyridinium p-toluenesulfonate.
- Verma, Sanny,Jain, Suman L.,Sain, Bir
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experimental part
p. 2314 - 2318
(2011/05/02)
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- Graphene oxide: An efficient and reusable carbocatalyst for aza-Michael addition of amines to activated alkenes
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Graphene oxide was found to be a highly efficient, reusable and cost-effective organocatalyst for the aza-Michael addition of amines to activated alkenes to furnish corresponding β-amino compounds in excellent yields. The Royal Society of Chemistry 2011.
- Verma, Sanny,Mungse, Harshal P.,Kumar, Neeraj,Choudhary, Shivani,Jain, Suman L.,Sain, Bir,Khatri, Om P.
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supporting information; experimental part
p. 12673 - 12675
(2012/01/05)
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- Silicon tetrachloride catalyzed aza-michael addition of amines to conjugated alkenes under solvent-free conditions
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The efficient and very simple conjugate addition of aromatic and aliphatic amines to α,β-unsaturated carbonyl compounds under solvent-free conditions in the presence of catalytic amount of silicon tetrachloride is reported. The reaction of aryl and alkyl amines with different Michael acceptors gave the corresponding Michael adducts with simple catalyst and good to excellent yields. Georg Thieme Verlag Stuttgart New York.
- Azizi, Najmedin,Baghi, Roya,Ghafuri, Hossein,Bolourtchian, Mohammad,Hashemi, Mohammad
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experimental part
p. 379 - 382
(2010/04/03)
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- Promiscuous Candida antarctica lipase B-catalyzed synthesis of β-amino esters via aza-Michael addition of amines to acrylates
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An efficient protocol for the regioselective aza-Michael addition of amines with acrylates using CaL B as a biocatalyst at 60 °C has been developed. The reaction is applicable to a wide variety of primary and secondary amines with different acrylates to synthesize the corresponding β-amino esters with good yields. An alternative route for the synthesis of higher β-amino esters through the additional transesterification step is also studied and was found effective.
- Dhake, Kishor P.,Tambade, Pawan J.,Singhal, Rekha S.,Bhanage, Bhalchandra M.
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experimental part
p. 4455 - 4458
(2010/09/20)
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- Highly efficient procedure for the conjugate addition of amines to electron deficient alkenes
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The novel efficient procedure has been developed for the conjugate addition of amines to electron deficient alkenes. The results showed that the catalyst was very efficient for the reactions with the excellent yields in several minutes. Operational simplicity, without need of any solvent, low cost of the catalyst used, high yields, reusability, excellent chemoselectivity, applicability to large-scale reactions are the key features of this methodology. The article is published in the original.
- Liao, An-Ping,Lan, Ping,Li, Mei,Lan, Li-Hong
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experimental part
p. 225 - 228
(2010/09/04)
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- Nanocrystalline copper(II) oxide catalyzed aza-Michael reaction and insertion of α-diazo compounds into N-H bonds of amines
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Nanocrystalline copper(II) oxide efficiently catalyzed the conjugate addition of aliphatic amines to α,β-unsaturated compounds to produce β-amino compounds with excellent yields under mild reaction conditions. Similarly, Glycine esters are obtained in good yields by the insertion of α-diazoacetate into N-H bonds of amines. The catalyst is used for three cycles with minimal loss of activity.
- Kantam, M. Lakshmi,Laha, Soumi,Yadav, Jagjit,Jha, Shailendra
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experimental part
p. 4467 - 4469
(2009/12/01)
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- Solvent free base catalysis and transesterification over basic functionalised Metal-Organic Frameworks
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Metal-Organic Frameworks (post-)functionalised with nitrogen containing moieties undergo solvent free aza-Michael condensation and transesterification, surpassing molecular and functionalised MCM-type analogues. The Royal Society of Chemistry 2009.
- Savonnet, Marie,Aguado, Sonia,Ravon, Ugo,Bazer-Bachi, Delphine,Lecocq, Vincent,Bats, Nicolas,Pinel, Catherine,Farrusseng, David
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experimental part
p. 1729 - 1732
(2011/03/20)
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- Vanadyl(IV) acetate: An efficient, reusable heterogenous catalyst for Aza-Michael reaction under solvent-free conditions
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Vanadyl(IV) acetate [VO(OAc)2] efficiently catalyzes the conjugate addition of aliphatic, aromatic amines to α,β-unsaturated carbonyl compounds in solvent-free media at room temperature to afford corresponding amino compounds in good to excellent yields. The catalyst can be recovered and reused for further cycles. Copyright Taylor & Francis Group, LLC.
- Trivedi, Rajiv,Lalitha,Roy, Sarabindu
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p. 3556 - 3566
(2008/12/23)
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- Borax as an efficient metal-free catalyst for hetero-Michael reactions in an aqueous medium
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Borax, a naturally occurring material, very efficiently catalyzed the conjugate addition of thiols, dithiols and amines to α,β-unsaturated ketones, nitriles, amides, aldehydes and esters in an aqueous medium to afford the corresponding Michael adducts in good yields at room temperature. Recycling of the catalyst and scaling up of the reactions are important attributes of this catalysis. The reactions of thiols and dithiols were relatively more facile than those of the corresponding amines. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Hussain, Sahid,Bharadwaj, Saitanya K.,Chaudhuri, Mihir K.,Kalita, Harjyoti
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p. 374 - 378
(2007/10/03)
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- Cellulose-supported copper(0) catalyst for aza-Michael addition
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Cellulose-supported copper(0) efficiently catalyzes the aza-Michael reaction of N-nucleophiles, such as amines and imidazoles with α,β-unsaturated compounds to produce the corresponding β-amino compounds and N-substituted imidazoles in excellent yields. The reactions are facile and the recovered catalyst is used for several cycles with consistent activity. Georg Thieme Verlag Stuttgart.
- Reddy, K. Rajender,Kumar, Nadakudity S.
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p. 2246 - 2250
(2007/10/03)
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- Polyvinyl pyridine as a novel solid heterogeneous, recyclable catalyst for aza-Michael reaction
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Polyvinyl pyridine (PVP) is prepared by radical polymerization of 4-vinyl pyridine. PVP was used as a heterogeneous basic catalyst for the aza-Michael reaction of secondary amines and carbamates with α,β-unsaturated esters, cyanides and ketones to obtain the corresponding adducts in excellent yields (70-90%). Georg Thieme Verlag Stuttgart.
- Raje, Vivek P.,Bhat, Ramakrishna P.,Samant, Shriniwas D.
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p. 2676 - 2678
(2008/09/16)
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- Cu(acac)2 immobilized in ionic liquids: A recoverable and reusable catalytic system for aza-Michael reactions
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Copper(II) acetylacetonate immobilized in ionic liquids efficiently catalyzes the aza-Michael reaction of amines with α,β-unsaturated carbonyl compounds to produce the corresponding β-amino carbonyl compounds with great alacrity in excellent yields. The reactions are far more facile than those reported earlier. The recovered ionic liquid phase containing the copper catalyst can be reused for several cycles with consistent activity.
- Kantam, M. Lakshmi,Neeraja,Kavita,Neelima,Chaudhuri, Mihir K.,Hussain, Sahid
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p. 763 - 766
(2007/10/03)
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- Boric acid: A novel and safe catalyst for aza-Michael reactions in water
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Boric acid efficiently catalyzes the conjugate addition of aliphatic amines to α,β-unsaturated compounds to produce β-amino compounds, with great alacrity and excellent yields, in water under mild conditions. Aromatic amines do not participate effectively in the reaction.
- Chaudhuri, Mihir K.,Hussain, Sahid,Kantam, M. Lakshmi,Neelima
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p. 8329 - 8331
(2007/10/03)
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- Efficient Copper-Catalyzed Chemo Selective Conjugate Addition of Aliphatic Amines to α,β-Unsaturated Compounds in Water
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The first environmentally benign, highly efficient, conjugate addition of aliphatic amines to α,β-unsaturated compounds catalyzed by simple copper salts in the green solvent, water is described.
- Xu, Li-Wen,Li, Jing-Wei,Xia, Chun-Gu,Zhou, Shao-Lin,Hu, Xiao-Xue
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p. 2425 - 2427
(2007/10/03)
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- Diesters of carbonic acid endowed with antiviral and anti-inflammatory activity
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Diesters of carbonic acid disubstituted with primary, secondary or tertiary amine groups, pharmaceutically acceptable salts thereof, and their use as antiviral and inti-inflammatory agents.
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