- Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source
-
We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.
- Zou, Qizhuang,Long, Guangcai,Zhao, Tianxiang,Hu, Xingbang
-
supporting information
p. 1134 - 1138
(2020/03/11)
-
- Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst
-
Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.
- Mitsudome, Takato,Miyagawa, Kazuya,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Yamasaki, Jun,Kitagawa, Yasutaka,Kaneda, Kiyotomi
-
supporting information
p. 9381 - 9385
(2017/08/01)
-
- Ruthenium-Catalyzed Methylation of Amines with Paraformaldehyde in Water under Mild Conditions
-
Methylated amines are highly important for a variety of pharmaceutical and agrochemical applications. Existing routes for their formation result in the production of large amounts of waste or require high reaction temperatures, both of which impact the ecological and economical footprint of the methodologies. Herein, we report the ruthenium-catalyzed reductive methylation of a range of aliphatic amines, using paraformaldehyde as both substrate and hydrogen source, in combination with water. This reaction proceeds under mild aqueous reaction conditions. Additionally the use of a secondary phase for catalyst retention and recycling has been investigated with promising results.
- van der Waals, Dominic,Heim, Leo. E.,Gedig, Christian,Herbrik, Fabian,Vallazza, Simona,Prechtl, Martin H. G.
-
p. 2343 - 2347
(2016/10/24)
-
- Glycerol as a Building Block for Prochiral Aminoketone, N-Formamide, and N-Methyl Amine Synthesis
-
Prochiral aminoketones are key intermediates for the synthesis of optically active amino alcohols, and glycerol is one of the main biomass-based alcohols available in industry. In this work, glycerol was catalytically activated and purposefully converted with amines to generate highly valuable prochiral aminoketones, as well as N-formamides and N-methyl amines, over CuNiAlOx catalyst. The catalyst structure can be anticipated as nano-Ni species on or in CuAlOx via the formation of nano- Cu?Ni alloy particles. This concept may present a novel and valuable methodology for glycerol utilization.
- Dai, Xingchao,Rabeah, Jabor,Yuan, Hangkong,Brückner, Angelika,Cui, Xinjiang,Shi, Feng
-
p. 3133 - 3138
(2016/11/29)
-
- N-Methylation of amines with methanol in a hydrogen free system on a combined Al2O3-mordenite catalyst
-
N-Methyl amines play a major role in the production of medicines, pesticides, surfactants and dyes. N-Methylation of primary or second amines with methanol is considered to be a green path for the synthesis of N-methyl amines and the catalyst is key. In this article, the combined Al2O3-mordenite catalyst (mass fraction of alumina is 40%) with good activity, selectivity, lifetime and stability was prepared for N-methylation of various amines with methanol in a hydrogen free system in a fixed bed reactor, and characterized by XRD, N2 adsorption and NH3-TPD. Furthermore, the methanol adsorption was investigated by in situ FTIR, and the result indicated that methoxyl species may be the active species for the N-methylation of amines.
- Su, Jiahui,Li, Xungang,Chen, Yunbin,Cui, Yuancun,Xu, Jingwei,Qian, Chao,Chen, Xinzhi
-
p. 55643 - 55649
(2016/07/06)
-
- SULFIDE SCAVENGERS, METHODS FOR MAKING AND METHODS FOR USING THEM
-
Methods for making sulfide scavenging compositions are provided. The method comprises reacting at least one secondary amine with at least one aldehyde and solvent in the presence of a catalyst to form a reaction composition, wherein a reaction temperature is less than or equal to 90 °C. Sulfide scavengers using the above method are also disclosed. Methods for removing sulfides from fluid streams are also provided. The methods include adding the above sulfide scavengers to fluid streams.
- -
-
Paragraph 0063
(2013/07/19)
-
- A practical regioselective synthesis of alkylthio- or arylthioindoles without the use of smelly compounds such as thiols
-
A convenient method for the synthesis of 3-methylthioindoles has been established which does not use smelly compounds such as thiol derivatives. The method, which introduces an alkyl- or arylthio-group into the C3-position of the indole skeleton, was extended to the direct introduction of a methylthio or bromo group at the C2-position using 3-methylthioindoles. No dimerization occurred, and the reaction mechanism was confirmed. The products have the partial structure of potent anti-methicillin-resistant Staphylococcus aureus (anti-MRSA) bromomethylthioindoles (MC 5-8) isolated from marine algae. Furthermore, this reaction could be applied to the synthesis of 3,3-diindolyl thioether which is a core structure of Echinosulfone A.
- Hamashima, Toshihiko,Mori, Yoshiaki,Sawada, Kazunori,Kasahara, Yuko,Murayama, Daisuke,Kamei, Yuto,Okuno, Hiroaki,Yokoyama, Yuusaku,Suzuki, Hideharu
-
p. 292 - 303
(2013/05/08)
-
- Investigation of the stability of quaternary ammonium methyl carbonates
-
Quaternary ammonium compounds are used commercially for a variety of applications and some are of interest as ionic liquids. For many years dimethyl carbonate has been touted as a green reagent, including its use for methylation (quaternization) of tertiary amines. In addition, substitution of the methyl carbonate by other anions can be efficiently and cleanly accomplished by reaction with the corresponding acid. How stable are these methyl carbonate quaternary compounds? High field 13C NMR shows that in the presence of water, the methyl carbonate is converted to bicarbonate. Headspace GCMS indicates that the alkylammonium methyl carbonate salts are stable below 170-180 °C while the bicarbonate salts are stable to only about 140 °C. Thermal decomposition occurs by decarboxylation and by dealkylation. AOCS 2011.
- Weisshaar, Duane E.,Earl, Gary W.,Amolins, Michael W.,Mickalowski, Kyle L.,Norberg, Justin G.,Rekken, Brian D.,Burgess, Angela M.,Kaemingk, Bethany D.,Behrens, Katherine C.
-
experimental part
p. 199 - 205
(2012/06/16)
-
- Dialkylamino and nitrogen heterocyclic analogues of hexadecylphosphocholine and cetyltrimetylammonium bromide: Effect of phosphate group and environment of the ammonium cation on their biological activity
-
A series of dialkylamino and nitrogen heterocyclic analogues of hexadecylphosphocholine and cetyltrimethylammonium bromide have been synthesized. The prepared compounds exhibit significant cytotoxic, antifungal and antiprotozoal activities. Alkylphosphocholines possess higher antifungal activity against Candida albicans in comparison with quaternary ammonium compounds. However, quaternary ammonium compounds exhibit significant higher activity against human tumor cells and Acanthamoeba lugdunensis compared to alkylphosphocholines. In addition, their haemolytic toxicity has been investigated. The relationship between structure and biological activity of the tested compounds is discussed.
- Lukac, Milos,Mojzis, Jan,Mojzisova, Gabriela,Mrva, Martin,Ondriska, Frantisek,Valentova, Jindra,Lacko, Ivan,Bukovsky, Marian,Devinsky, Ferdinand,Karlovska, Janka
-
scheme or table
p. 4970 - 4977
(2010/02/27)
-
- A novel strategy for oligopeptide synthesis using a polymer-supported ammonium fluoride
-
A novel method for the preparation of oligopeptides with a PS-ammonium fluoride in the solution phase is reported. The synthesis of lipid II pentapeptide is efficiently synthesized via a PS-ammonium fluoride without chromatographic purifications. The method reported here is very convenient to synthesize a relatively large amount of oligopeptides with abundantly available Fmoc-protected amino acids in a time efficient manner.
- Kurosu, Michio,Crick, Dean C.
-
p. 5325 - 5328
(2007/10/03)
-
- Process for the synthesis of N-methyl-dialkylamines from secundary amines and formaldehyde
-
Production of N-methyldialkylamines comprises reacting a dialkylamine with 1.5-3 molar equivalents of formaldehyde at 100-200[deg]C; degassing the reaction product; separating the aqueous phase; and distilling the organic phase.
- -
-
Page column 5
(2008/06/13)
-
- Reaction of aliphatic amines with 49% formic acid. 1-hexylamine, di-1-hexylamine, N,N-dimethyl-1-hexylamine, 1-dodecylamine, N,N-dimethyl-1-dodecylamine and N,N-dimethyl-1-butylamine
-
Two primary amines, 1-hexylamine 2, 1-dodecylamine 19, one secondary amine, di-1-hexylamine 18, and three tertiary amines, N,N-dimethyl-1-hexylamine 6, N,N-dimethyl-1-butylamine 3, and N,N-dimethyl-1-dodecylamine 22 were each heated at 150°C, 250°C or 350°C with 49% aqueous formic acid for varying periods of time. The aliphatic primary amines underwent easy N-formylation and subsequent reduction to give N-methyl- and N,N-dimethylalkylamines. Especially at higher temperatures, other reactions intervened including elimination of NH3 to the corresponding alkenes followed by partial double bond isomerization. Tertiary amines were more reactive at higher temperatures undergoing hydrolysis and reductive cleavages to secondary and primary amines, which subsequently followed the reaction sequences seen for primary amines. This series of saturated amines showed none of the cleavage into smaller fragments that was observed in the reductive alkylation of pyridine and 4-methylpyridine to a series of N-alkylpiperdines. This result reinforces the bis-aza-retro-Aldol-fragmentation mechanism postulated for the formation of the N-alkylpiperidines. Johann Ambrosius Barth 1997.
- Katritzky, Alan R.,Parris, Roslyn L.,Ignatchenko, Elena S.,Allin, Steven M.,Siskin, Michael
-
-
- Fast N-methylation of amines under microwave irradiation
-
Primary and secondary amines are quickly N-methylated by methanal and formic acid under microwave irradiation.
- Barbry, Didier,Torchy, Severine
-
p. 3919 - 3922
(2007/10/03)
-
- Organomagnesium Inner Complexes, Part I. Bis(dialkylaminoalkyl)- and Bis(alkoxybutyl)magnesium Compounds
-
A series of magnesium inner complexes has been prepared by reacting MgH2 (prepared by homogeneous catalysis) with dialkylallyl- and -3-butenylamines and -3-butenylethers in the presence of catalytic amounts of ZrCl4.The monomeric nature of bis(4-methoxybutyl)magnesium has been confirmed by X-ray diffraction.The analogous syntheses of bis(3-alkoxypropyl)magnesium compounds failed: cleavage of the allyl ether with elimination of propene occurred.This cleavage reaction is accelerated by catalytic amounts of NiCl2 or ZrCl4. - Keywords: Magnesium, Inner Complexes, Crystal Structure, X-Ray
- Angermund, Klaus,Bogdanovic, Borislav,Koppetsch, Gudrun,Krueger, Carl,Mynott, Richard,et al.
-
p. 455 - 466
(2007/10/02)
-
- SPECIFIC ACID CATALYSIS IN THE DECOMPOSITION OF TRIALKYLTRIAZENES.
-
The acid-catalyzed decomposition of 1,3-di-n-butyl-3-methyltriazene (1) in aqueous buffer was investigated. Determination of the kinetics over a pH range of 10. 4 to 12 indicated that the reaction is acid catalyzed. Variation of buffer concentration, at constant ionic strength, produced an insignificant variation in the rate constant. The determination of kinetics of the decomposition of 1 in nine different buffers, ranging in pK//a from 9. 6 to 12. 7, also gave negligible variation in the rate constants. The solvent isotope effect for the reaction, k//H/k//D, was 0. 62. These data strongly support the conclusion that the reaction is specific acid catalyzed. This implies that the reaction involves fast, reversible protonation of the triazene followed by the rate-determining heterolysis of the protonated species to n-butyldiazonium ion and n-butylmethylamine.
- Smith Jr.,Denlinger,Kupper,Koepke,Michejda
-
p. 1056 - 1059
(2007/10/02)
-
- THE HOMOGENEOUSLY CATALYSED SYNTHESIS OF N-METHYLDIALKYLAMINES FROM N-METHYL AND N,N-DIMETHYLALKYLAMIMES
-
N-Methyl and N,N-dimethylalkylamines are converted into N-methyldialkylamines in good yields when heated at 180 deg C in the presence of a catalytic amount of RuCl2(Ph3P)3.
- Arcelli, Antonio,Bui-The-Khai,Porzi, Gianni
-
p. C31 - C34
(2007/10/02)
-
- SELECTIVE CONVERSION OF PRIMARY AMINES INRO N,N-DIMETHYLALKYL- OR N,N-DIALKYLMETHYL-AMINES WITH METHANOL AND RuCl2(Ph3P)3
-
N,N-dimethylalkyl- or N,N-dialkylmethyl-amines are selectively obtained from the reaction between aliphatic amines and methanol at 180 deg C for 7 h in the presence of RuCl2(Ph3P)3 catalyst.
- Arcelli, Antonio,Khai, Bui-The,Porzi, Gianni
-
-