- 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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- Synthesis and catalytic activity of porous polymer containing ionic liquid structures
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A novel porous polymer containing ionic liquid (IL) structures was synthesized via quternization and condensation of 4-vinylpyridine and p-xylylene dichloride. The ionic liquid structures were incorporated in the polymeric framework and for this reason bulky IL molecules can hardly block pores and neutralize active sites. The polymer shows a high BET surface area and easily accessible active sites. Catalytically the polymer is very active in Michael additions with averaged yields over 96.0% achieved after short reaction times. The high BET surface, remarkable activity, operational simplicity, wide applicability and improved stability are the key properties of the polymer.
- Li, Junqiao,Lu, Wei,Li, Weifeng,Liang, Xuezheng
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p. 840 - 846
(2016/12/07)
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- Synthesis of a crosslinked polymer with a benzyl(triphenyl)phosphonium ionic liquid moiety and its catalytic activity
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A novel crosslinked polymer with a benzyl(triphenyl)phosphonium ionic liquid moiety was synthesized from triphenylphosphine and p-xylylene dichloride. The bulky IL molecules were inlaid in the polymeric framework, which avoided pore blocking and IL moiety release. The polymer had a high BET surface area and accessible active sites. The polymer was applied to catalyze the aza-Michael additions and gave average yields over 95.0% in several minutes. The polymer had several advantages such as high BET surface area, high activity and high stability, which hold great potential for green chemical processes.
- Liang, Xuezheng
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p. 99448 - 99453
(2015/12/04)
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- Design and evaluation of switchable-hydrophilicity solvents
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Switchable-hydrophilicity solvents (SHSs) are solvents that can switch reversibly between one form that is miscible with water to another that forms a biphasic mixture with water. For these SHSs, we use CO2 at 1 bar as a stimulus for triggering the transformation to the water-miscible form and removal of CO2 to achieve the reverse. We now report the identification of 13 new SHSs, including the first secondary amine SHSs, and a comparison of all known SHSs in terms of safety and environmental impacts. Amines which include another functional group, especially oxygen-containing groups, are less hazardous than alkylamines. Secondary amines can have improved switching speeds relative to tertiary amines. The variety of SHSs identified suggests that amine SHSs can be designed to have ideal properties for a given application.
- Vanderveen, Jesse R.,Durelle, Jeremy,Jessop, Philip G.
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p. 1187 - 1197
(2014/03/21)
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- Ecofriendly and efficient procedure for hetero-Michael addition reactions with an acidic ionic liquid as catalyst and reaction medium
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1-Methylimidazolium trifluoroacetate ([Hmim]-TFA) is reported as a cost-effective catalyst for a simple and environmentally benign hetero-Michael reaction. [Hmim]TFA works both as reaction medium and catalyst. The reaction is applicable to various aromatic sulfur and nitrogen nucleophiles. This method has advantages such as high yields, short reaction time, and simple workup. The catalyst could be recycled several times without any loss of activity.
- Dabiri, Minoo,Salehi, Peyman,Bahramnejad, Mahboobeh,Baghbanzadeh, Mostafa
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experimental part
p. 109 - 112
(2012/06/30)
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- Cesium fluoride catalyzed Aza-Michael addition reaction in aqueous media
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A green approach to the Aza-Michael addition reaction between an amine and α,β-unsaturated compounds has been achieved by conventional as well as non-conventional methods. The reaction is catalyzed by cesium fluoride (CsF) in aqueous media at ambient temperature to afford the product in excellent yield. Ultrasound irradiation has been used as a non-conventional energy source, which reduces the reaction time with improved product yield.
- Labade, Vilas B.,Pawar, Shivaji S.,Shingare, Murlidhar S.
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experimental part
p. 1055 - 1059
(2012/07/27)
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- Crown ether complex cation ionic liquids: Preparation and applications in organic reactions
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A series of crown ether complex cation ionic liquids (CECILs) were designed, synthesised and characterised by NMR spectroscopy, HRMS, thermogravimetric differential thermal analysis (TG-DTA) and elemental analysis. Their applications in various organic reactions were investigated: [15-C-5Na][OH], [15-C-5Na][OAc], [18-C-6K][OH] and [18-C-6K][OAc] (15-C-5=[15]crown-5; 18-C-6=[18]crown-6) efficiently catalysed the Michael addition of alkenes and relevant nucleophiles; [18-C-6K][OH] and [15-C-5Na][OH] effectively catalysed the Henry reaction of nitromethane and aromatic aldehydes; [18-C-6K][OH] has excellent catalytic efficiency for Knoevenagel condensation of aromatic aldehydes and malononitrile; PdCl2/[18-C-6K] 3[PO4]/K2CO3 efficaciously catalysed the Heck reaction of olefins and aromatic halides; [18-C-6K][BrO3] can be used as both oxidant and solvent in the oxidation reaction of aromatic alcohols. The CECIL catalysts [15-C-5Na][OH] (Michael addition) and [18-C-6K][OH] (Henry reaction) can be recycled and reused several times without obvious loss of activity and their recovery is very simple.
- Song, Yingying,Jing, Huanwang,Li, Bo,Bai, Dongsheng
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experimental part
p. 8731 - 8738
(2011/09/16)
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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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- A comparison between nickel and palladium precatalysts of 1,2,4-triazole based N-heterocyclic carbenes in hydroamination of activated olefins
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A comparison is drawn between the nickel and palladium precatalysts of 1,2,4-triazole based N-heterocyclic carbenes in the hydroamination of activated olefins. Though all of the newly designed nickel and palladium precatalysts, trans-[1-i-propyl-4-R-1,2,4-triazol-5-ylidene]2MBr2 [R = Et, M = Ni (1b); R = Et, M = Pd (1c); R = CH2CHCH2, M = Ni (2b) and R = CH2CHCH2, M = Pd (2c)], are moderately active for hydroamination reaction of a variety of secondary amines viz. morpholine, piperidine, pyrrolidine and diethylamine with activated olefins like, acrylonitrile, methyl acrylate, ethyl acrylate and t-butyl acrylate at room temperature in 1 hour, the nickel complexes (1b and 2b) exhibited superior activity compared to its palladium counterparts (1c and 2c). The better performance of the nickel complexes has been correlated to the more electron deficient metal center in the nickel 1b and 2b complexes than in the palladium 1c and 2c analogs based on the density functional theory studies. The 1b-c and 2b-c complexes were synthesized by the reaction of 1-i-propyl-4-R-1,2,4- triazolium bromide [R = Et (1a) and R = CH2CHCH2 (2a)] with MCl2 [M = Ni, Pd] in presence of NEt3 as a base. The Royal Society of Chemistry 2010.
- Dash, Chandrakanta,Shaikh, Mobin M.,Butcher, Ray J.,Ghosh, Prasenjit
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experimental part
p. 2515 - 2524
(2010/05/14)
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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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- N-donor ligand as catalyst: A simple Aza-Michael addition reaction in aqueous media
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(Chemical Equation Presented) A novel approach for the Aza-Michael addition reactions between various amines and α,β-unsaturated esters, nitriles and ketones using N-donor Ligand catalyst (3 mol %) is described. The reactions are carried out in aqueous media at an ambient temperature to afford the products in excellent yields.
- Pawar, Shivaji S.,Dekhane, Deepak V.,Shingare, Murlidhar S.,Thore, Shivaji N.
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experimental part
p. 1869 - 1873
(2009/06/18)
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- Samarium(III) triflate catalyzed conjugate addition of amines to electron-deficient alkenes
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Amines undergo smooth nucleophilic addition to α,β-unsaturated compounds in the presence of a catalytic amount of samarium(III) triflate at ambient temperature to produce the corresponding β-amino compounds in excellent yields. This method is simple, convenient, and works efficiently under mild conditions. Georg Thieme Verlag Stuttgart.
- Yadav,Ramesh Reddy,Gopal Rao,Narsaiah,Subba Reddy
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p. 3447 - 3450
(2008/09/19)
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- Palladium-catalyzed C-N bond activation: The synthesis of β-amino acid derivatives from triethylamine and acrylates
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In the palladium-catalyzed reaction of acrylates, C-N bond activation and acetalization occurred under different conditions. Described herein is a highly efficient palladium-catalyzed C-N bond activation reaction and subsequent new C-N bond formation to directly construct β-amino acids from triethylamine and acrylate esters in isolated yields of up to 95%. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Zou, Bo,Jiang, Huan-Feng,Wang, Zhao-Yang
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p. 4600 - 4604
(2008/02/12)
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- Addition of secondary amines to α,β-unsaturated carbonyl compounds and nitrites by using microstructured reactors
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Several additions of amines to α,β-unsaturated carbonyl compounds (Michael additions) were performed in a continuous-flow microstructured reactor rig and compared to the respective batch reaction. Dimethylamine/diethylamine/piperidine and acrylic acid ethyl ester/acrylonitrile were employed as two sets of reactants, giving six reactions. Some of these reactions are highly exothermal. Using the traditional batch procedure the olefin must be added quite slowly to the diluted amine to ensure temperature control and safe operation; especially this is necessary for the addition of dimethylamine (40 mass % aqueous solution) to acrylonitrile. Good yields (>85%) are achieved in this way; however, processing time is very long (17-25 h). To reveal the intrinsic kinetic potential and thus to accelerate these reactions, the reactants were mixed in a continuous-flow microstructured reactor rig which allows rapid mixing and efficient removal of the reaction heat. In this way, reaction time was decreased to a few seconds up to about half an hour, which is a change by 2 orders of magnitude. While the yields achieved with the continuous-flow microstructured reactor rig matched those for the batch procedure, the space-time yields for the microflow processing are much higher, in the best case by a factor of about 650.
- Loewe,Hessel,Lob,Hubbard
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p. 1144 - 1152
(2012/12/23)
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- Structure-activity relationship of trihexyphenidyl analogs with respect to the dopamine transporter in the on going search for a cocaine inhibitor
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A series of trihexyphenidyl (THP) analogs were used to search for a derivative that could serve as a cocaine inhibitor. A compound that blocks binding of the cocaine analog carboxyfluorotropane (CFT), allows dopamine uptake and exhibits low side effects could serve as a good candidate for that purpose. All analogs were tested for the extent to which they inhibit CFT binding, dopamine uptake and n-methyl scopolamine (NMS) binding. Several structure-function relationships emerged. Methylation/halogenation of THP's benzene ring enhanced the compound's ability to block CFT binding in comparison to its ability to block dopamine uptake (5a-e). Replacement of the cyclohexyl ring with a benzene ring tended to create compounds that had lower affinities to the dopamine transporter (7b compared to THP, 7d compared to 5h, 7c compared to 8c) and modification of THP's piperidine ring tended to enhance affinity to the dopamine transporter (5f-h, 8a, 8c). One analog (5f) that showed little muscarinic activity indicating that it would probably have few side effects was investigated for its effects as an in vivo cocaine inhibitor. However, it showed few antagonistic effects in vivo. Nevertheless, this work greatly elucidates the structure-function relationships required for potential cocaine inhibitors and so lays out promising directions for future research.
- Dar,Thiruvazhi,Abraham,Kitayama,Kopajtic,Gamliel,Slusher,Carroll,Uhl
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p. 1013 - 1021
(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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- Clay catalyzed chemoselective Michael type addition of aliphatic amines to α,β-ethylenic compounds
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Application of acidic clays as heterogeneous catalysts for the Michael type addition reaction of aliphatic amines to α,β-ethylenic compounds is presented. Aromatic amines do not participate in this transformation.
- Shaikh, Nadim S.,Deshpande, Vishnu H.,Bedekar, Ashutosh V.
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p. 9045 - 9048
(2007/10/03)
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- Bis(pyrimidine)-based palladium catalysts: Synthesis, X-ray structure and applications in Heck-, Suzuki-, Sonogashira-Hagihara couplings and amination reactions
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The synthesis of N,N-bis(pyrimid-2-yl)amine (1), N-acetyl-N,N-bis(pyrimid-2-yl)amide (2), N-norborn-2-ene-5-ylbis(pyrimid-2-yl)carbamide (4) is described. The Pd-complex N-acetyl-N,N-bis(pyrimid-2-yl)amine palladium dichloride (3) has been prepared from compound 2 and its X-ray structure has been determined. A polymer supported catalytic system (6) was prepared via ring-opening metathesis copolymerization of 4 with 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo-endo-dimethanonaphthalene (HDMN-6) and subsequent loading with PdCl2. Both the homogeneous and heterogeneous catalysts 3 and 6 were active in Heck-, Suzuki-, Sonogashira-Hagihara-type couplings and amination reactions using aryl iodides, bromides and chlorides.
- Buchmeiser, Michael R.,Schareina, Thomas,Kempe, Rhett,Wurst, Klaus
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- Water promoted Michael addition of secondary amines: To α,β- unsaturated carbonyl compounds under microwave irradiation
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A rapid Michael addition of secondary amines to α,β-unsaturated carbonyl compounds has been achieved in good to excellent yields in the presence of water under microwave irradiation. In the absence of water and under conventional method the reaction does not proceed or take place in very low yield after a long reaction time.
- Matloubi Moghaddam, Firouz,Mohammadi, Mohsen,Hosseinnia, Azarmidocht
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p. 643 - 650
(2007/10/03)
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- Tandem conjugate addition-aldol reaction to α,β-unsaturated esters and ketones using titanium amide
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Titanium dialkylamide, readily available, adds to a α,β-unsaturated esters and ketones in a conjugate addition mode to give ester and ketone enolates, respectively, which are successively quenched with electrophiles such as aldehydes and acetals. The aldol products can be readily converted to the corresponding deaminated or dehydrated derivatives selectively.
- Hosomi, Akira,Yanagi, Toshiharu,Hojo, Makoto
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p. 2371 - 2374
(2007/10/02)
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- CATALYSIS OF THE SPECIFIC MICHAEL ADDITION : THE EXAMPLE OF ACRYLATE ACCEPTORS
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Lewis acids, ferric chloride in particular, catalyze the addition of amine nucleophiles to arcylates.Yields are very good, under mild conditions.Exlusive 1,4-addition occurs, and polymerization is avoided.
- Cabral, Jose,Laszlo, Pierre,Mahe, Loic,Montaufier, Marie-Therese,Randriamahefa, S. Lalatiana
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p. 3969 - 3972
(2007/10/02)
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- Action d'organometalliques fonctionnels sur des gem-aminoethers et des sels d'immonium. I. Synthese d'amines α- ou β-fonctionnelles difficilement accessibles par reaction de Mannich
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Some α- or β-functional amines which are difficult to obtain by Mannich reaction can be easily prepared from organomagnesium or organozinc functional derivatives and gem-aminoethers or immonium salts.
- Courtois, Gilles,Miginiac, Philippe
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p. 395 - 400
(2007/10/02)
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- Beta-amino carbonyl catalysts for polyurethane preparation
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Provided as catalysts for the formation of cellular urethane polymers ranging from flexible to rigid foams, are beta-amino carbonyl compounds wherein carbonyl is present as an amido or carboxylic acid ester group and the beta-amino group is present as dialkylamino or an N-morpholino or N,N'-piperazino heterocyclic nucleus. Effective in the catalysis of the water-isocyanate reaction, these beta-amino amides and beta-amino esters are used with particular advantage in the manufacture of water-blown flexible foams, both molded and free-rise, including high-resilience and flame-retarded foam. The beta-amino carbonyl catalysts allow for the formation of foam products essentially free of the odor associated with amines such as N-ethylmorpholine. In view of this highly desirable characteristic and their other beneficial properties, the catalysts of the invention are advantageously employed as direct replacements for N-ethylmorpholine in high-resilience and other foam formulations.
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